CN107761046B - A kind of fused salt electroreduction method that infiltration yttrium in aluminium copper surface is modified - Google Patents

A kind of fused salt electroreduction method that infiltration yttrium in aluminium copper surface is modified Download PDF

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CN107761046B
CN107761046B CN201711098682.4A CN201711098682A CN107761046B CN 107761046 B CN107761046 B CN 107761046B CN 201711098682 A CN201711098682 A CN 201711098682A CN 107761046 B CN107761046 B CN 107761046B
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liyf
lif
yttrium
alloy
temperature
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CN107761046A (en
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王旭
王瑞祥
廖春发
焦芸芬
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Jiangxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
    • C23C10/20—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions only one element being diffused
    • C23C10/24—Salt bath containing the element to be diffused
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/02—Pretreatment of the material to be coated

Abstract

The present invention relates to aluminium copper surfaces to seep yttrium modification technology, and specifically Applied Electrochemistry method penetrates into method of the yttrium to improve surface erosion resistance on aluminium copper surface.The present invention is the following steps are included: (1) matches raw material, (2) pre-oxidation, (3) purification, (4) electroreduction infiltration yttrium, (5) surface treatment.The aluminium copper surface for seeping yttrium is tested through 240h copper acetate salt fog (CASS), 2.0~6.0mm of unilateral Erosion Width range, better than the unilateral Erosion Width of ZL203 (8.0~10.0mm) without seeping yttrium processing.

Description

A kind of fused salt electroreduction method that infiltration yttrium in aluminium copper surface is modified
Technical field
The present invention relates to aluminium copper surfaces to seep yttrium modification technology, and specifically Applied Electrochemistry method is on aluminium copper surface Penetrate into method of the yttrium to improve surface erosion resistance.
Background technique
Al-Cu class alloy is the cast aluminium alloy industrially used earliest, and main performance and characteristics are room temperature and high-temperature mechanics Can be high, casting technique is simple, and machinability is good, fine heat-resisting performance, is to develop high-strength aluminum alloy containing Cu and various resistance to The basis of thermalloy, but the disadvantage is that the casting character of based solid solution alloys is poor, corrosion resistance is low, therefore limits aluminum bronze binary The application field of alloy.
Summary of the invention
The object of the present invention is to provide a kind of aluminium copper surfaces to seep the modified fused salt electroreduction method of yttrium, it is by aoxidizing Object (Y2O3) pass through the side that Y element is penetrated into ZL203 (copper mass content 4-5%, surplus are aluminium) alloy surface by fused salt electrochemical reduction method Method.
Technical solution of the present invention: a kind of fused salt electroreduction method that infiltration yttrium in aluminium copper surface is modified, including following step It is rapid:
(1) raw material are matched:
With anhydrous LiYF4, LiF be basic electrolyte, Y2O3For the donor material of element Y, ZL203 alloy is to seep Y matrix material Material；
Ratio requirement:
LiYF4, LiF mixture account for seep Y system substance molar content be 99.2~99.5%, remaining is Y2O3, and LiYF4, LiF blending agent molar ratio LiYF4: LiF=9:1；
(2) it pre-oxidizes:
ZL203 alloy is placed in nitrogen and oxygen molar ratio is 1:9, pressure 1atm, 500~550 DEG C of temperature of atmosphere furnace 0.5~1.0h of middle oxidation, then be cooled to room temperature in air；
(3) it purifies:
By the raw material LiYF in step (1)4-LiF-Y2O3It is sufficiently mixed, melts under the conditions of 600 DEG C~650 DEG C of temperature Change, 2h is kept the temperature under the conditions of 100~500Pa of vacuum degree, is passed through argon gas protection in removing system after moisture；
(4) electroreduction seeps yttrium:
The LiYF that step (3) are purified4-LiF-Y2O3Melt is protected through argon gas, in 600~650 DEG C of temperature, voltage 4.5 ~4.8V, 0.3~0.5A/cm of current density2Under the conditions of, electroreduction seeps 1~2h of yttrium, takes out ZL203 alloy substrate later in argon It is cooled to room temperature in gas, wherein cathode is the ZL203 alloy substrate of pre-oxidation, and anode is graphite；
(5) it is surface-treated:
After ZL203 alloy surface removal particle and burr that step (4) electroreduction is seeped to yttrium, wash with distilled water again through 80 DEG C temperature dries 1h.
Main control condition and foundation:
1, pre-oxidation guarantees that alloy substrate has enough oxidated layer thickness, while also controlling the thickness of permeable formation, mainly By the oxygen content (N of oxidizing atmosphere2With O2Molar ratio is 1:9), at 500~550 DEG C of temperature control oxidization time be 0.5~ 1.0h。
2, electric osmose guarantees that good Y layers of thickness structure of infiltration need 600~650 DEG C of strict temperature control range, voltage range 4.5 ~4.8V and 1~2h of electric osmose time.
Cost of material of the present invention is low, equipment is simple, can be with lower cost directly by Y2O3Oxide powder is by element Y The surface aluminium copper ZL203 is penetrated into, is tested through 240h copper acetate salt fog (CASS), 2.0~6.0mm of unilateral Erosion Width range, Better than the unilateral Erosion Width of ZL203 (8.0~10.0mm) without seeping yttrium processing.
Specific embodiment
Embodiment 1:LiYF4The molar content of-LiF is that 99.2% (remaining is Y2O3), and LiYF4: LiF=9:1 The anhydrous LiYF of (molar ratio)4-LiF-Y2O3Medium is sufficiently mixed, and is melted under the conditions of 650 DEG C of temperature, in vacuum degree 100Pa item 2h is kept the temperature under part, is passed through argon gas protection in removing system after moisture, and with this LiYF4-LiF-Y2O3Mixing melting system is electrolysis Matter；ZL203 alloy is in pressure 1atm, N2:O2In=1:9 (molar ratio) atmosphere, after 550 DEG C of oxidation 1.0h of temperature again in air It is cooled to room temperature, and is set to cathode, graphite is anode；In the LiYF of purification4-LiF-Y2O3In melt, protected through argon gas, In 650 DEG C of temperature, voltage 4.8V, current density 0.5A/cm2Under the conditions of after electroreduction seeps yttrium time 2h, then in argon gas it is cooling The ZL203 alloy that Y is seeped on surface is obtained to room temperature, the ZL203 alloy surface after seeping yttrium uses distilled water after removal particle and burr It cleans and obtains seeping y alloy product through 80 DEG C of drying 1h；It is tested through 240h copper acetate salt fog (CASS), unilateral Erosion Width 2.06mm, fine corrosion resistance are greatly improved compared with ZL203 alloy.
Embodiment 2:LiYF4The molar content of-LiF is that 99.3% (remaining is Y2O3), and LiYF4: LiF=9:1 The anhydrous LiYF of (molar ratio)4-LiF-Y2O3Medium is sufficiently mixed, and is melted under the conditions of 640 DEG C of temperature, in vacuum degree 200Pa item 2h is kept the temperature under part, is passed through argon gas protection in removing system after moisture, and with this LiYF4-LiF-Y2O3Mixing melting system is electrolysis Matter；ZL203 alloy is in pressure 1atm, N2:O2It is cold in air that 0.75h is aoxidized under=1:9 (molar ratio) atmosphere, at 520 DEG C of temperature But to being cathode after room temperature, graphite is anode；In the LiYF of purification4-LiF-Y2O3In melt, protected through argon gas, 640 DEG C of temperature, Voltage 4.7V, current density 0.4A/cm2, electroreduction is cooled to room temperature (25 DEG C) in argon gas and obtains table after seeping yttrium time 1.5h The ZL203 alloy of Y is seeped in face, and the ZL203 alloy surface after seeping yttrium passes through afterwards wash with distilled water after removal particle and burr processing 80 DEG C of drying 1h obtain seeping y alloy product.It is tested through 240h copper acetate salt fog (CASS), unilateral Erosion Width 3.20mm, corrosion resistant Function admirable is lost, is greatly improved compared with ZL203 alloy.
Embodiment 3:LiYF4The molar content of-LiF is that 99.4% (remaining is Y2O3), and LiYF4: LiF=9:1 The anhydrous LiYF of (molar ratio)4-LiF-Y2O3Medium is sufficiently mixed, and is melted under the conditions of 630 DEG C of temperature, in vacuum degree 300Pa item 2h is kept the temperature under part, is passed through argon gas protection in removing system after moisture, and with this LiYF4-LiF-Y2O3Mixing melting system is electrolysis Matter；ZL203 alloy is in pressure 1atm, N2:O2It is cold in air that 0.75h is aoxidized under=1:9 (molar ratio) atmosphere, at 530 DEG C of temperature But to being cathode after room temperature, graphite is anode；In the LiYF of purification4-LiF-Y2O3In melt, protected through argon gas, 630 DEG C of temperature, Voltage 4.6V, current density 0.4A/cm2, electroreduction, which seeps, to be cooled to room temperature to obtain surface after yttrium time 1.5h in argon gas and seeps Y's ZL203 alloy, the ZL203 alloy surface after seeping yttrium are dried through 80 DEG C afterwards wash with distilled water after removal particle and burr processing Dry 1h obtains seeping y alloy product.It is tested through 240h copper acetate salt fog (CASS), unilateral Erosion Width 4.25mm, corrosion resistance It is excellent, it is greatly improved compared with ZL203 alloy.
Embodiment 4:LiYF4The molar content of-LiF is that 99.4% (remaining is Y2O3), and LiYF4: LiF=9:1 The anhydrous LiYF of (molar ratio)4-LiF-Y2O3Medium is sufficiently mixed, and is melted under the conditions of 620 DEG C of temperature, in vacuum degree 400Pa item 2h is kept the temperature under part, is passed through argon gas protection in removing system after moisture, and with this LiYF4-LiF-Y2O3Mixing melting system is electrolysis Matter；ZL203 alloy is in pressure 1atm, N2:O2It is cold in air that 0.5h is aoxidized under=1:9 (molar ratio) atmosphere, at 520 DEG C of temperature But to being cathode after room temperature, graphite is anode；In the LiYF of purification4-LiF-Y2O3In melt, protected through argon gas, 620 DEG C of temperature, Voltage 4.6V, current density 0.4A/cm2, electroreduction, which seeps, to be cooled to room temperature to obtain surface after yttrium time 1.5h in argon gas and seeps Y's ZL203 alloy, the ZL203 alloy surface after seeping yttrium are dried through 80 DEG C afterwards wash with distilled water after removal particle and burr processing Dry 1h obtains seeping y alloy product.It is tested through 240h copper acetate salt fog (CASS), unilateral Erosion Width 5.18mm, corrosion resistance It is excellent, it is greatly improved compared with ZL203 alloy.
Embodiment 5:LiYF4The molar content of-LiF is that 99.5% (remaining is Y2O3), and LiYF4: LiF=9:1 The anhydrous LiYF of (molar ratio)4-LiF-Y2O3Medium is sufficiently mixed, and is melted under the conditions of 600 DEG C of temperature, in vacuum degree 500Pa item 2h is kept the temperature under part, is passed through argon gas protection in removing system after moisture, and with this LiYF4-LiF-Y2O3Mixing melting system is electrolysis Matter；ZL203 alloy is in pressure 1atm, N2:O2It is cold in air that 0.5h is aoxidized under=1:9 (molar ratio) atmosphere, at 500 DEG C of temperature But to being cathode after room temperature, graphite is anode；In the LiYF of purification4-LiF-Y2O3In melt, protected through argon gas, 600 DEG C of temperature, Voltage 4.5V, current density 0.3A/cm2, electroreduction, which seeps, to be cooled to room temperature to obtain surface after yttrium time 1h in argon gas and seeps Y's ZL203 alloy, the ZL203 alloy surface after seeping yttrium are dried through 80 DEG C afterwards wash with distilled water after removal particle and burr processing Dry 1h obtains seeping y alloy product.It is tested through 240h copper acetate salt fog (CASS), unilateral Erosion Width 6.01mm, corrosion resistance It is excellent, it is greatly improved compared with ZL203 alloy.

Claims (2)

1. the modified fused salt electroreduction method of yttrium is seeped on a kind of aluminium copper surface, characterized in that the following steps are included:
(1) raw material are matched:
With anhydrous LiYF4, LiF be basic electrolyte, Y2O3For the donor material of element Y, ZL203 alloy is to seep Y basis material；
Ratio requirement:
Anhydrous LiYF4, LiF mixture account for seep Y system substance molar content be 99.2~99.5%, remaining is Y2O3, and nothing Water LiYF4, LiF blending agent molar ratio LiYF4: LiF=9:1；
(2) it pre-oxidizes:
ZL203 alloy is placed in nitrogen and oxygen molar ratio as oxygen in 1:9, pressure 1atm, 500~550 DEG C of temperature of atmosphere furnace Change 0.5~1.0h, then is cooled to room temperature in air；
(3) it purifies:
By the anhydrous LiYF of raw material in step (1)4- LiF-Y2O3It is sufficiently mixed, melts under the conditions of 600 DEG C~650 DEG C of temperature Change, 2h is kept the temperature under the conditions of 100~500Pa of vacuum degree, is passed through argon gas protection in removing system after moisture；
(4) electroreduction seeps yttrium:
The anhydrous LiYF that step (3) are purified4- LiF-Y2O3Melt is protected through argon gas, in 600~650 DEG C of temperature, voltage 4.5~4.8V, 0.3~0.5A/cm of current density2Under the conditions of, electroreduction seeps 1~2h of yttrium, takes out ZL203 alloy substrate later and exists It is cooled to room temperature in argon gas, wherein cathode is the ZL203 alloy substrate of pre-oxidation, and anode is graphite；
(5) it is surface-treated:
After ZL203 alloy surface removal particle and burr that step (4) electroreduction is seeped to yttrium, wash with distilled water again through 80 DEG C of temperature Degree drying 1h.
2. the modified fused salt electroreduction method of yttrium, specific implementation are seeped in a kind of aluminium copper surface according to claim 1 are as follows: By anhydrous LiYF4The molar content of-LiF is 99.2%, remaining is Y2O3, and anhydrous LiYF4: LiF molar ratio=9:1 LiYF4- LiF-Y2O3Medium is sufficiently mixed, and is melted under the conditions of 650 DEG C of temperature, is kept the temperature 2h under the conditions of vacuum degree 100Pa, Argon gas protection is passed through in removing system after moisture, and with this anhydrous LiYF4- LiF-Y2O3Mixing melting system is electrolyte； ZL203 alloy is in pressure 1atm, N2: O2It is cooled in air again in molar ratio=1:9 atmosphere, after 550 DEG C of oxidation 1.0h of temperature Room temperature, and it is set to cathode, graphite is anode；In the anhydrous LiYF of purification4- LiF-Y2O3In melt, protected through argon gas, In 650 DEG C of temperature, voltage 4.8V, current density 0.5A/cm2Under the conditions of after electroreduction seeps yttrium time 2h, then in argon gas it is cooling The ZL203 alloy that Y is seeped on surface is obtained to room temperature, the ZL203 alloy surface after seeping yttrium uses distilled water after removal particle and burr It cleans and obtains seeping y alloy product through 80 DEG C of drying 1h；It is tested through 240h copper acetate salt fog CASS, unilateral Erosion Width 2.06mm, fine corrosion resistance are greatly improved compared with ZL203 alloy.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4979314A (en) * 1972-12-08 1974-07-31
CN104775137A (en) * 2014-01-13 2015-07-15 赣州飞腾轻合金有限公司 Method for preparing aluminum-samarium interalloy through liquid-state cathode salt fusion electrolysis method
CN104962954A (en) * 2015-07-30 2015-10-07 江西理工大学 Method for preparing rare earth-aluminum-copper interalloy by fused salt electrolysis and alloy thereof
CN105177632A (en) * 2015-07-30 2015-12-23 江西理工大学 Molten salt electrolysis method for preparing copper-aluminum-rare earth intermediate alloy in rare-earth modification manner and alloy
CN106834905A (en) * 2016-12-16 2017-06-13 包头稀土研究院 Rare earth ferroalloy and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4979314A (en) * 1972-12-08 1974-07-31
CN104775137A (en) * 2014-01-13 2015-07-15 赣州飞腾轻合金有限公司 Method for preparing aluminum-samarium interalloy through liquid-state cathode salt fusion electrolysis method
CN104962954A (en) * 2015-07-30 2015-10-07 江西理工大学 Method for preparing rare earth-aluminum-copper interalloy by fused salt electrolysis and alloy thereof
CN105177632A (en) * 2015-07-30 2015-12-23 江西理工大学 Molten salt electrolysis method for preparing copper-aluminum-rare earth intermediate alloy in rare-earth modification manner and alloy
CN106834905A (en) * 2016-12-16 2017-06-13 包头稀土研究院 Rare earth ferroalloy and preparation method thereof

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