An 8YSZ: (Eu 3+ &Tb 3+ ) thermosensitive ceramic material and a preparation method thereof

Abstract

The application discloses a preparation method of 8YSZ:(Eu 3+ &Tb 3+ ) temperature-sensitive ceramic material. The application takes ZrOCl2*8H2O, Y2O3, Eu2O3 and Tb4O7 as raw materials, NH3*H2O as a reaction bottom liquid, polyethylene glycol as a dispersant, hydrogen peroxide as an oxidant, and successfully prepares 8YSZ:(Eu 3+ &Tb 3+ ) temperature-sensitive ceramic material through a chemical coprecipitation method. The experimental method adopted by the application is easy to operate, low in cost, easy to control, multiple in controllable variables, and repeatable. The obtained 8YSZ:(Eu 3+ &Tb 3+ ) temperature-sensitive ceramic material has good luminescent performance, temperature-sensitive performance and fluorescent decay life and the like advantages. The application provides a good foundation for development of thermal barrier coating materials, and provides a good design idea for fluorescent performance research of multi-rare earth element doped temperature-sensitive ceramic materials, and the good fluorescent and temperature-sensitive performance can be better applied to real-time monitoring of service temperatures of the thermal barrier coating materials, so that the application has a wide application prospect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of preparation of temperature-sensitive ceramic materials and luminescence, and particularly relates to a kind of 8YSZ:(Eu 3+ &Tb 3+ ) temperature-sensitive ceramic materials and a preparation method thereof. BACKGROUND

[0002] The hot end components of an aero-engine are operated in a harsh environment of high temperature, high pressure and smoke for a long time, and a series of complex "thermal problems" are inevitable. At present, the thermal barrier coating (TBCs) system used by most turbine blades of an aero-engine mainly consists of four parts, i.e., an alloy substrate, an MCrAlY or Pt modified aluminide bonding layer, a thermal growth oxide (TGO) and a yttria-stabilized zirconia (YSZ) ceramic layer. The service life of the thermal barrier coating depends largely on the TGO and the YSZ ceramic layer. However, the working temperature of the TGO and the YSZ ceramic layer largely determines their service life. Therefore, temperature monitoring is very important for the thermal barrier coating. The principle of the fluorescence temperature measurement technology with optical response temperature characteristics is that the rare earth fluorescent material with temperature self-sensitivity is excited by heat, and the excited energy is released in the form of fluorescence during the recovery process of the outer electron from the excited state to the ground state, and the fluorescence intensity and wavelength have the correlation characteristics with temperature changes. The loss of the coating can be evaluated by detecting the change of the fluorescence intensity, so that the service life of the coating can be non-destructively studied.

[0003] When the rare earth ions absorb energy, the 4f and 5d configurations will produce the electron transition behavior, including f-f electron transition and f-d electron transition. The spectrum of 4f-5d electron transition is mainly band-shaped, and f-d transition needs higher energy than f-f transition and produces strong luminescence intensity. The rare earth ions Tm 3+ , Eu 3+ and Tb 3+ , etc. can realize 4f-5d electron transition. The charge transfer transition is not inhibited by the selection rule, and the charge transfer can be realized in the rare earth ions Eu 3+ , Tm 3+ and Tb 3+ , etc., so that a wide continuous spectrum is induced. The YSZ ceramic material doped with a single rare earth element has been studied more before, and they all show good fluorescence performance in a narrow wavelength range, and the fluorescence lifetime is relatively general. The YSZ ceramic material doped with multiple elements and its preparation need to be further studied. SUMMARY

[0004] The application aims to provide a kind of 8YSZ:(Eu 3+ &Tb 3+ ) temperature-sensitive ceramic material, which is mainly used for thermal barrier coating material and has good thermal and temperature-sensitive performance.

[0005] Another object of the present application is to provide a preparation method of 8YSZ:(Eu 3+ &Tb 3+ ) temperature sensitive ceramic material. Specifically comprising the following steps.

[0006] (1) According to the different doping amount of Tb and Eu, the corresponding ZrOCl2·8H2O, Y2O3, Eu2O3 and Tb4O7 are weighed.

[0007] (2) ZrOCl2·8H2O powder is dissolved in deionized water to obtain solution A, and Y2O3, Tb4O7 and Eu2O3 mixed drugs are dissolved in a certain amount of 1 mol / L dilute hydrochloric acid and hydrogen peroxide solution to obtain solution B.

[0008] (3) Mix solution AB and stir magnetically for 30 min, then add polyethylene glycol and continue to stir for 30 min. Add ammonia solution to the obtained solution to obtain white precipitate, measure the pH value during the addition, ensure that the pH value of the reaction bottom liquid is always 10, then let the solution stand for 15 h, until the reaction is complete and the system is stable, then use a centrifuge, wash with deionized water three times and then with anhydrous ethanol twice.

[0009] (4) Dry the washed and filtered object, grind thoroughly after complete drying, put it into a muffle furnace (box furnace) for firing, grind thoroughly after cooling, and finally obtain 8YSZ:(Eu 3+ &Tb 3+ ) ceramic powder.

[0010] Preferably, the amount of polyethylene glycol used in step (3) of the present application is 3% of the total weight of the added substances.

[0011] Preferably, the firing temperature and time of the powder in step (4) of the present application are 800℃ and 6h.

[0012] The purity of ZrOCl2·8H2O, Y2O3, Eu2O3 and Tb4O7 in the present application is ≥99.99%.

[0013] The beneficial effects of the present application are:

[0014] (1) The method of the present application can refine the particle size of the material, and the 8YSZ:(Eu 3+ &Tb 3+ ) temperature sensitive ceramic material prepared has good luminescent performance, and the fluorescence performance of the powder changes regularly according to the different doping amount of Tb.

[0015] (2) The 8YSZ:(Eu 3+ &Tb 3+The fluorescent performance of the temperature-sensitive ceramic material regularly changes with temperature, and has good absolute sensitivity and relative sensitivity. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 8YSZ:Eu prepared for Example 4 3+ &Tb 3+ XRD diagram of the temperature-sensitive ceramic material.

[0017] Figure 2 8YSZ:Eu prepared for Example 4 3+ &Tb 3+ SEM diagram of the temperature-sensitive ceramic material.

[0018] Figure 3 8YSZ:Eu prepared for Example 4 3+ &Tb 3+ Excitation spectrum diagram of the temperature-sensitive ceramic material.

[0019] Figure 4 8YSZ:Eu prepared for Examples 1, 2, 3, 4, 5 3+ &Tb 3+ Emission spectrum diagram of the temperature-sensitive ceramic material.

[0020] Figure 5 8YSZ:Eu prepared for Example 4 3+ &Tb 3+ Fluorescence decay lifetime diagram of the temperature-sensitive ceramic material.

[0021] Figure 6 8YSZ:Eu prepared for Example 4 3+ &Tb 3+ Variable-temperature spectrum diagram of the temperature-sensitive ceramic material.

[0022] Figure 7 8YSZ:Eu prepared for Example 4 3+ &Tb 3+ Absolute sensitivity and relative sensitivity diagram of the temperature-sensitive ceramic material. DETAILED DESCRIPTION

[0023] The application will be further described in conjunction with specific embodiments, but these embodiments do not limit the scope of the application in any way.

[0024] Example 1

[0025] A preparation method of an 8YSZ:(Eu 3+ &Tb 3+ ) temperature-sensitive ceramic material, comprising the following operations:

[0026] Take 4.6053 g of ZrOCl2·8H2O, 0.1412 g of Y2O3 and 0.0275 g of Eu2O3. Dissolve ZrOCl2·8H2O in deionized water, dissolve Y2O3, Eu2O3 and Tb4O7 in 1 mol / L dilute hydrochloric acid solution, then add a certain amount of hydrogen peroxide solution, stir and stand respectively, and after complete dissolution, mix the solutions and stir for 30 min using a magnetic stirrer; then add polyethylene glycol dispersant and continue stirring for 30 min. At the same time, prepare the reaction bottom solution of ammonia water, add concentrated ammonia water into a beaker and adjust its pH to 10 with deionized water, and leave it for standby use. After the mother liquor is stirred, add the mixed solution and concentrated ammonia water into the reaction bottom solution drop by drop, and keep the pH of the solution at 10 during the reaction until the reaction is completed. After the reaction is completed, continue stirring for 30 min, then stand for 15 h or more to obtain the precipitate of the mixture. Then pour the precipitate of the mixture into a centrifuge tube, add deionized water, and put it into a centrifuge with a speed of 8000 rpm for 3 min. After centrifugation, pour off the supernatant, continue to add deionized water, and repeat the above operation 3 to 5 times until the solution is neutral, then centrifuge twice with anhydrous ethanol. Place the sample after centrifugation in a blast drying oven, and dry at 60℃ for 15 h, then take it out, grind it thoroughly with a mortar, place the thoroughly ground powder in a crucible, and put it into a muffle furnace to calcine at a temperature of 800℃ for 6 h, then take it out, grind it thoroughly, and obtain 8YSZ:(Eu 3+ &Tb 3+ ) ceramic powder.

[0027] Example 2

[0028] A preparation method of an 8YSZ:(Eu 3+ &Tb 3+ ) temperature-sensitive ceramic material, comprising the following operations:

[0029] Take 4.5990 g of ZrOCl2·8H2O, 0.1412 g of Y2O3, 0.0275 g of Eu2O3 and 0.0146 g of Tb4O7. Dissolve ZrOCl2·8H2O in deionized water, dissolve Y2O3, Eu2O3 and Tb4O7 in 1 mol / L dilute hydrochloric acid solution, then add a certain amount of hydrogen peroxide solution, stir and stand respectively, and after complete dissolution, mix the solution and stir for 30 min using a magnetic stirrer; then add polyethylene glycol dispersant and continue stirring for 30 min. At the same time, prepare the reaction bottom solution of ammonia water, add concentrated ammonia water into a beaker and adjust its pH to 10 with deionized water, and leave it for standby use. After the mother liquor is stirred, add the mixed solution and concentrated ammonia water into the reaction bottom solution drop by drop, and keep the pH of the solution at 10 during the reaction until the reaction is completed. After the reaction is completed, continue stirring for 30 min, then stand for 15 h or more to obtain the precipitate of the mixture. Then pour the precipitate of the mixture into a centrifuge tube, add deionized water, and put it into a centrifuge with a speed of 8000 rpm for 3 min. After centrifugation, pour off the supernatant, continue to add deionized water, and repeat the above operation 3 to 5 times until the solution is neutral, then centrifuge twice with anhydrous ethanol. After centrifugation, the sample is placed in a blast drying oven, dried at 60℃ for 15 h, then taken out, ground thoroughly with a mortar, and the ground powder is placed in a crucible and calcined in a muffle furnace at a temperature of 800℃ for 6 h, then taken out, ground thoroughly, and 8YSZ:(Eu 3+ &Tb 3+ ) ceramic powder is obtained.

[0030] Example 3

[0031] A preparation method of an 8YSZ:(Eu 3+ &Tb 3+ ) temperature-sensitive ceramic material, comprising the following operations:

[0032] Take 4.5927 g of ZrOCl2·8H2O, 0.1412 g of Y2O3, 0.0275 g of Eu2O3 and 0.0292 g of Tb4O7. Dissolve ZrOCl2·8H2O in deionized water, dissolve Y2O3, Eu2O3 and Tb4O7 in 1 mol / L dilute hydrochloric acid solution, then add a certain amount of hydrogen peroxide solution, stir and stand respectively, and after complete dissolution, mix the solution and stir for 30 min using a magnetic stirrer; then add polyethylene glycol dispersant and continue stirring for 30 min. At the same time, prepare the reaction bottom solution of ammonia water, add concentrated ammonia water into a beaker and adjust its pH to 10 with deionized water, and leave it for standby use. After the mother liquor is stirred, add the mixed solution and concentrated ammonia water into the reaction bottom solution drop by drop, and keep the pH of the solution at 10 during the reaction until the reaction is completed. After the reaction is completed, continue stirring for 30 min, then stand for 15 h or more to obtain the precipitate of the mixture. Then pour the precipitate of the mixture into a centrifuge tube, add deionized water, and put it into a centrifuge with a speed of 8000 rpm for 3 min. After centrifugation, pour off the supernatant, continue to add deionized water, and repeat the above operation 3 to 5 times until the solution is neutral, then centrifuge twice with anhydrous ethanol. After centrifugation, the sample is placed in a blast drying oven, dried at 60℃ for 15 h, then taken out, ground thoroughly with a mortar, and the ground powder is placed in a crucible and calcined in a muffle furnace at a temperature of 800℃ for 6 h, then taken out, ground thoroughly, and 8YSZ:(Eu 3+ &Tb 3+ ) ceramic powder is obtained.

[0033] Example 4

[0034] A preparation method of an 8YSZ:(Eu 3+ &Tb 3+ ) temperature sensitive ceramic material, comprising the following operations:

[0035] According to the stoichiometric ratio, 4.5864 g of ZrOCl2·8H2O, 0.1412 g of Y2O3, 0.0275 g of Eu2O3 and 0.0438 g of Tb4O7 are weighed. ZrOCl2·8H2O is dissolved in deionized water, Y2O3, Eu2O3 and Tb4O7 are dissolved in 1 mol / L dilute hydrochloric acid solution, then a certain amount of hydrogen peroxide solution is added, and stirred and placed respectively. After complete dissolution, the mixed solution is stirred for 30 min using a magnetic stirrer. Then polyethylene glycol dispersant is added and stirring is continued for 30 min. At the same time, the reaction bottom solution of ammonia water is prepared. Concentrated ammonia water is added to a beaker, and deionized water is used to adjust the pH to 10, and is kept for standby use. After the mother liquor is stirred, the mixed solution and concentrated ammonia water are added dropwise into the reaction bottom solution respectively, and the pH of the solution is kept at 10 during the reaction until the reaction is completed. After the reaction is completed, stirring is continued for 30 min, and then it is placed for 15 h or more to obtain the precipitate of the mixture. Then the precipitate of the mixture is poured into a centrifuge tube, deionized water is added, and it is placed in a centrifuge with a speed of 8000 rpm for 3 min. After centrifugation, the supernatant is discarded, deionized water is continuously added, and the above operation is repeated for 3 to 5 times until the solution is neutral, and then it is centrifuged twice with anhydrous ethanol. The sample after centrifugation is placed in a blast drying oven, and is dried at 60°C for 15 h. Then it is taken out, ground thoroughly with a mortar, and the ground powder is placed in a crucible and calcined in a muffle furnace at a temperature of 800°C for 6 h. Then it is taken out, ground thoroughly, and 8YSZ:(Eu 3+ &Tb 3+ ) ceramic powder is obtained.

[0036] Example 5

[0037] A preparation method of an 8YSZ:(Eu 3+ &Tb 3+ ) temperature sensitive ceramic material, comprising the following operations:

[0038] According to the stoichiometric ratio, 4.5801 g of ZrOCl2·8H2O, 0.1412 g of Y2O3, 0.0275 g of Eu2O3 and 0.0584 g of Tb4O7 were weighed. ZrOCl2·8H2O was dissolved in deionized water, Y2O3, Eu2O3 and Tb4O7 were dissolved in 1 mol / L dilute hydrochloric acid solution, then a certain amount of hydrogen peroxide solution was added, and stirred and settled respectively. After complete dissolution, the mixed solution was stirred for 30 min by using a magnetic stirrer; then polyethylene glycol dispersant was added and continued to stir for 30 min. At the same time, the reaction bottom solution of ammonia water was prepared. Concentrated ammonia water was added to a beaker, and the pH was adjusted to 10 with deionized water, and was kept for standby use. After the mother liquor was stirred, the mixed solution and concentrated ammonia water were added dropwise into the reaction bottom solution respectively, and the pH of the solution was kept at 10 during the reaction until the end of the reaction. After the reaction was completed, continue to stir for 30 min, and then stand for 15 h or more to obtain the precipitate of the mixture. Then the precipitate of the mixture was poured into a centrifuge tube, deionized water was added, and the centrifuge was set at a speed of 8000 rpm and centrifuged for 3 min. After centrifugation, the supernatant was discarded, deionized water was continuously added, and the above operation was repeated for 3 to 5 times until the solution was neutral, and then centrifuged twice with anhydrous ethanol. The sample after centrifugation was placed in a blast drying oven, and dried at 60℃ for 15 h, then taken out, ground thoroughly with a mortar, and the ground powder was placed in a crucible and calcined in a muffle furnace at a temperature of 800℃ for 6 h, then taken out, ground thoroughly, and 8YSZ:(Eu 3+ &Tb 3+ ) ceramic powder was obtained.

[0039] The 8YSZ:(Eu 3+ &Tb 3+ ) temperature-sensitive ceramic material was tested by XRD, and it can be found from the attached Figure 1 that compared with the XRD pattern of 8YSZ:Eu 3+ ceramic material, the pattern of 8YSZ:(Eu 3+ &Tb 3+ ) is basically the same, indicating that 8YSZ:(Eu 3+ &Tb 3+ ) is still a stable tetragonal phase structure at room temperature. Through SEM test, it can be found from the attached Figure 2 that the particles of 8YSZ:(Eu 3+ &Tb 3+ ) ceramic powder are spherical or elliptical, the particle size is about 20 nm, the sphericity of the particles is good, the crystallinity is high, the surface is smooth, and the distribution is uniform, but a small amount of agglomerates can still be observed. The 8YSZ:(Eu 3+ &Tb 3+ ) temperature-sensitive ceramic material was tested by fluorescence and temperature-sensitive performance, and it can be found from the attachedFigure 4 It can be seen from FIG. 6 that the luminescence intensity of the powder first increases and then decreases with the increase of the doping amount of Tb at the excitation wavelength of 285 nm, and the luminescence intensity at 543 nm is as high as 1949748.5 (a.u.). From FIG. 7, it can be seen that the luminescence intensity of the powder first increases and then decreases with the increase of the doping amount of Tb at the excitation wavelength of 285 nm, and the luminescence intensity at 543 nm is as high as 1949748.5 (a.u.). Figure 5 The fluorescence decay lifetime of the material of Example 4 is calculated to be 2.38 ms. From FIG. 8, it can be seen that the fluorescence decay lifetime of the material of Example 4 is 2.38 ms. Figure 6 And 7 It can be seen from FIG. 6 that the luminescence intensity of the powder first increases and then decreases with the increase of the doping amount of Tb at the excitation wavelength of 285 nm, and the luminescence intensity at 543 nm is as high as 1949748.5 (a.u.). From FIG. 7, it can be seen that the luminescence intensity of the powder first increases and then decreases with the increase of the doping amount of Tb at the excitation wavelength of 285 nm, and the luminescence intensity at 543 nm is as high as 1949748.5 (a.u.). 3+ &Tb 3+ It can be seen from FIG. 6 that the luminescence intensity of the powder first increases and then decreases with the increase of the doping amount of Tb at the excitation wavelength of 285 nm, and the luminescence intensity at 543 nm is as high as 1949748.5 (a.u.). From FIG. 7, it can be seen that the luminescence intensity of the powder first increases and then decreases with the increase of the doping amount of Tb at the excitation wavelength of 285 nm, and the luminescence intensity at 543 nm is as high as 1949748.5 (a.u.). A (8YSZ:Eu 3+ &Tb 3+ ) = 0.48% K -1 @ 350 K, and the absolute sensitivity S R (8YSZ:Eu 3+ &Tb 3+ ) = 0.54% K -1 @ 350 K. From the above results, it can be seen that the 8YSZ:(Eu 3+ &Tb 3+ ) temperature-sensitive ceramic material has good fluorescence and temperature-sensitive properties, and can be applied to

Claims

1. A method of producing an 8YSZ:(Eu 3+ &Tb 3+ ) thermosensitive ceramic material, characterized by, Prepared by chemical co-precipitation method, the main steps are as follows: (1) according to the different doping amount of Tb and Eu, the corresponding ZrOCl2·8H2O, Y2O3, Eu2O3 and Tb4O7 are weighed; (2) using deionized water to dissolve ZrOCl2·8H2O powder to obtain solution A, using a certain amount of 1mol / L dilute hydrochloric acid and hydrogen peroxide solution to dissolve Y2O3, Tb4O7, Eu2O3 mixed chemicals to obtain solution B; (3) mix solution AB and electromagnetic stirring for 30 min, then add polyethylene glycol, continue to stir for 30 min, add ammonia solution to the obtained solution to obtain white precipitate, measure the pH value while adding, ensure that the pH value of the reaction bottom liquid is always 10, then let the solution stand for 15 h, until the reaction is complete and the system is stable, use centrifuge, wash with deionized water for three times, then wash with anhydrous ethanol for two times; The amount of polyethylene glycol in step (3) is weighed according to 3% of the total weight of the added substances; (4) The washed and filtered object is dried, and after drying is complete, it is thoroughly ground, placed in a muffle furnace, and fired. After cooling, it is again thoroughly ground, and 8YSZ:(Eu 3+ &Tb 3+ ) ceramic powder is obtained. The powder sintering temperature and time in step (4) are: 800℃, 6h.

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