CN110628423B - Oxysulfide elastic stress luminescent material and preparation method thereof - Google Patents

Oxysulfide elastic stress luminescent material and preparation method thereof Download PDF

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CN110628423B
CN110628423B CN201910955682.4A CN201910955682A CN110628423B CN 110628423 B CN110628423 B CN 110628423B CN 201910955682 A CN201910955682 A CN 201910955682A CN 110628423 B CN110628423 B CN 110628423B
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oxysulfide
luminescent material
stress luminescent
elastic stress
elastic
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庄逸熙
陈昌健
周天亮
解荣军
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Xiamen University
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Abstract

An oxysulfide elastic stress luminescent material and a preparation method thereof, belonging to the field of inorganic luminescent materials. The chemical expression general formula of the oxysulfide elastic stress luminescent material is Sr1‑xZn2‑ yS2O:Ax,ByWherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 2, x and y represent molar percentage content, and x and y are not zero at the same time; a is at least one of rare earth ions Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm or Yb and the like; b is at least one of transition metal ions Mn or Cu. Preparation: weighing the raw materials of the metal elements according to the stoichiometric ratio, grinding and uniformly mixing the raw materials in an agate pot, placing the mixed powder in an alumina crucible, heating to 800-1200 ℃ under a protective atmosphere or vacuum, preserving heat for 10-48 h, and naturally cooling to room temperature along with the furnace; and grinding the cooled powder to obtain the oxysulfide elastic stress luminescent material.

Description

Oxysulfide elastic stress luminescent material and preparation method thereof
Technical Field
The invention belongs to the field of inorganic luminescent materials, and particularly relates to an oxysulfide elastic stress luminescent material and a preparation method thereof.
Background
A stress luminescence (ML) material refers to a solid material that produces luminescence under various mechanical forces such as extrusion, friction, impact, stretching, twisting. The stress luminescent materials are classified into destructive fracture stress luminescent materials and non-destructive deformation stress luminescent materials according to the degree of deformation and whether the materials are recoverable, and the non-destructive deformation stress luminescent materials are further classified into elastic stress luminescent materials and plastic stress luminescent materials. The elastic stress luminescence has the advantages of repeatability, light intensity proportional to stress, high sensitivity and the like, and has great application potential in the fields of building structure flaw detection, electronic signature systems, electronic skins and the like.
Since the peculiar phenomenon that Bacon et al occasionally found stress luminescence when cutting square candy in 1605, the researchers of materials have carried out a lot of work on the aspects of composition, structure, mechanism and application of stress luminescent materials, and have found a lot of stress luminescent materials. Unfortunately, most of the stress luminescent materials belong to fracture stress luminescence or plastic stress luminescence, and the stress luminescence intensity of most of the materials is very weak, so that the stress luminescence materials cannot be applied to practical productionIn life. The stress luminescent materials which are applied at present are elastic stress luminescent materials, and the types are limited to the following types: SrAl2O4Eu (green), ZnS, Mn (yellow); ZnS: Cu (blue-green light), CaZnOS: Mn (red light), etc. Currently, the research on elastic stress luminescent materials mainly has the following problems: (1) the variety of elastic stress luminescent materials with recoverability is less; (2) the known elastic stress luminescent material has more luminescent intensity and is difficult to meet the application requirement; (3) the mechanism of the stress luminescent material is not clear, and the development and design of the stress luminescent material are difficult.
Disclosure of Invention
The present invention aims at providing one kind of elastic stress oxysulfide luminescent material and its preparation process.
The chemical expression general formula of the oxysulfide elastic stress luminescent material is Sr1-xZn2-yS2O:Ax,ByWherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 2, x and y represent molar percentage content, and x and y are not zero at the same time; a is at least one of rare earth ions Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm or Yb and the like; b is at least one of transition metal ions Mn or Cu.
Preferably, the oxysulfide elastic stress luminescent material has the composition that x is more than or equal to 0 and less than or equal to 0.05, y is more than or equal to 0 and less than or equal to 0.1, and x and y are not zero at the same time.
The crystal structure of the oxysulfide elastic stress luminescent material belongs to an orthorhombic system.
The oxysulfide elastic stress luminescent material can generate stress luminescence by directly applying stress to the oxysulfide elastic stress luminescent material without the need of pre-ultraviolet light or visible light irradiation.
The oxysulfide elastic stress luminescent material does not need to be irradiated by ultraviolet light or visible light in advance, stress is applied to powder of the oxysulfide elastic stress luminescent material, or stress is applied to a film or a cylinder prepared by mixing the powder and an elastic high polymer material, and stress luminescence occurs within the elastic limit of the material.
The stress applied to the oxysulfide elastic stress luminescent material includes, but is not limited to, mechanical action of friction, compression, tension, complete, impact, torsion, ultrasound, and the like.
The stress luminous intensity of the oxysulfide elastic stress luminescent material is in a linear relation with the applied stress.
A method for preparing an oxysulfide elastic stress luminescent material comprises the following steps:
1) sr adopts oxide, hydroxide or carbonate thereof as a raw material, Zn adopts sulfide thereof as a raw material, rare earth ions adopt oxide, fluoride, nitrate or carbonate thereof as a raw material, transition metal ions adopt oxide, nitrate and carbonate thereof as a raw material, and each metal element is weighed according to the stoichiometric ratio thereof and ground and uniformly mixed in an agate pot to obtain mixed powder;
2) placing the mixed powder ground in the step 1) into an alumina crucible, heating to 800-1200 ℃ under protective atmosphere or vacuum, preserving heat for 10-48 h, and naturally cooling to room temperature along with the furnace;
3) grinding the powder cooled in the step 2) to obtain the oxysulfide elastic stress luminescent material Sr1-xZn2-yS2O:Ax,By。
In step 1), preferably, the Sr uses its carbonate as a raw material; the rare earth ions adopt oxides thereof as raw materials; the Mn adopts carbonate thereof as a raw material; the Cu adopts sulfide thereof as a raw material.
In the step 2), the protective atmosphere is pure argon atmosphere or pure nitrogen atmosphere.
Compared with the prior art, the invention has the following advantages and gain effects:
1) the invention adopts the traditional solid phase reaction method for preparation, has simple process, low equipment requirement, easy control of conditions, low cost, no generation of toxic and harmful substances in the preparation process and environmental protection.
2) The oxysulfide elastic stress luminescent material prepared by the invention can realize luminescence adjustable stress luminescence by doping different rare earth ions or transition metal ions.
3) The oxysulfide elastic stress luminescent material prepared by the invention has a direct proportion relation between the stress luminous intensity and the applied stress in a certain elastic range, and can be applied to the detection of stress distribution.
Drawings
FIG. 1 shows X-ray diffraction spectra of sample powders prepared in examples 1 to 3 of the present invention.
FIG. 2 shows emission spectra of samples prepared in examples 1 to 3 of the present invention.
FIG. 3 shows the tribo spectra of samples prepared in examples 1 to 3 of the present invention.
FIG. 4 is a graph of the stress luminescence intensity of the sample prepared in example 1 of the present invention fitted to the pressure.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited thereto.
Examples 1 to 3:
selecting strontium carbonate, zinc sulfide and transition metal carbonate or rare earth ion oxide as raw materials, weighing the raw materials according to the molar ratio of each element (specifically shown in table 1), putting the raw materials into an agate mortar for grinding, uniformly mixing, taking a proper amount of sample, putting the sample into a corundum crucible, putting the crucible into a corundum boat, pushing the corundum boat into a tubular furnace, heating to 1000 ℃ under the protection of pure argon gas, preserving heat for 24 hours, and naturally cooling along with the furnace. And grinding the cooled sample for 10-30 min to obtain the oxysulfide-based stress luminescent powder.
TABLE 1 sample ratios of examples 1-3
Figure BDA0002227212110000031
FIG. 1 is an X-ray diffraction pattern of samples prepared in examples 1 to 3, wherein the spectral line is measured by a Bruker d8-advance bruker X-ray diffractometer, the test voltage is 40kv, the test current is 40mA, Cu-Ka rays are selected, and the wavelength is
Figure BDA0002227212110000032
Figure BDA0002227212110000041
The X-ray diffraction analysis shows that SrZn can be obtained by calcining the sample at 1000 ℃ for 24h2S2The O pure phase belongs to an orthorhombic system, the formation of a crystal phase is not influenced by doping of transition metal Mn or rare earth ions Pr and Yb, and other mixed phases are not observed.
FIG. 2 shows the emission spectra of the samples prepared in examples 1 to 3, measured by an Edinburgh instruments FL980 steady-state and transient luminescence spectrometer, with a xenon lamp as the excitation light source, the data acquisition integration time of 0.2s, and the scanning step length of 1 nm. SrZn of the sample in example 1 under 270nm light excitation1.99S2O:Mn0.01Exhibits yellow luminescence with broad peak emission, the luminescence peak is 584nm, and is derived from Mn2+Electronic slave4T1(4G) To6A1(6S) energy level transition. Sample Sr in example 20.99Zn2S2O:Pr0.01Exhibits a linear spectrum in which 490nm and 510nm luminescence originates from Pr3+Electronic slave3P0To3H4And3H4670nm luminescence from Pr3+Electronic slave3P0To3F2Is detected. Sample Sr in example 30.99Zn2S2O:Yb0.01Shows linear near infrared emission with an emission peak of 980nm and belongs to Yb3+ electron3F5/2To2F7/2Is detected.
FIG. 3 is a friction spectrum of a sample prepared in examples 1 to 3, wherein sample powder is placed in an agate bowl, a glass rod is used for rubbing the sample to emit light, the light emission of the sample is collected by a marine optical fiber spectrometer QE pro, and the data acquisition integration time is 1 s. As shown in fig. 3, the samples all exhibited stress luminescence with the triboluminescence spectrum and the respective emission spectra remaining substantially the same.
FIG. 4 is a graph of the stress luminescence intensity versus pressure magnitude fitted to samples prepared from the samples of example 1. Adopting an Shimadzu AGS-X series electronic universal testing machine to carry out a pressure luminescence experiment, controlling the force within the range of 0-1800N, and adopting hamamatsu photon detectionThe detector C9692 collects the luminous intensity, and fits the luminous intensity and the stress intensity as shown in FIG. 4, and the goodness of fit R20.9941, indicating that the two exhibit a good linear relationship.
The invention discloses an oxysulfide elastic stress luminescent material Sr1-xZn2-yS2O:Ax,ByWherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 2, x and y represent molar percentage content, and x and y are not zero at the same time; a is one or more of rare earth ions Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm or Yb; b is one or two of transition metal ions Mn or Cu. The invention also discloses a preparation method of the oxysulfide elastic stress luminescent material, which comprises the following steps: (1) respectively weighing raw materials according to the element molar ratio; (2) grinding the raw materials weighed in the step (1) uniformly, and roasting in an inert atmosphere or vacuum; (3) and taking out the roasted sample, and grinding to obtain the oxysulfide elastic stress luminescent material. The elastic stress material has adjustable light-emitting wave band, higher light-emitting efficiency and simple preparation method, and has potential application value in the application fields of structural damage detection, electronic signature systems, electronic skins and the like which relate to stress monitoring.

Claims (9)

1. An oxysulfide elastic stress luminescent material is characterized in that the chemical expression general formula is Sr1-xZn2-yS2O:Ax,ByWherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 2, x and y represent molar percentage content, and x and y are not zero at the same time; a is at least one of rare earth ions Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm or Yb; b is at least one of transition metal ions Mn or Cu.
2. The oxysulfide elastic stress luminescent material according to claim 1, wherein x is 0. ltoreq. x.ltoreq.0.05, y is 0. ltoreq. y.ltoreq.0.1, and x and y are not zero at the same time.
3. The oxysulfide elastic stress luminescent material according to claim 1, wherein the crystal structure of the oxysulfide elastic stress luminescent material belongs to an orthorhombic system.
4. The oxysulfide elastic stress luminescent material according to claim 1, wherein the stress luminescence occurs within the elastic limit of the material by directly applying stress to the oxysulfide elastic stress luminescent material or by applying stress to a film or cylinder made by mixing the oxysulfide elastic stress luminescent material with an elastic polymer material.
5. The oxysulfide elastic stress luminescent material of claim 4, wherein the stress applied to said oxysulfide elastic stress luminescent material includes but is not limited to friction, compression, tension, impact, torsion, ultrasound.
6. The oxysulfide elastic stress luminescent material as claimed in claim 4, wherein the stress luminescence intensity of the oxysulfide elastic stress luminescent material is linearly related to the magnitude of the applied stress.
7. The method of claim 1, wherein the method comprises the steps of:
1) sr adopts oxide, hydroxide or carbonate thereof as a raw material, Zn adopts sulfide thereof as a raw material, rare earth ions adopt oxide, fluoride, nitrate or carbonate thereof as a raw material, transition metal ions adopt oxide, nitrate and carbonate thereof as a raw material, and each metal element is weighed according to the stoichiometric ratio thereof and ground and uniformly mixed in an agate pot to obtain mixed powder;
2) placing the mixed powder ground in the step 1) into an alumina crucible, heating to 800-1200 ℃ under protective atmosphere or vacuum, preserving heat for 10-48 h, and naturally cooling to room temperature along with the furnace;
3) grinding the powder cooled in the step 2) to obtain the oxysulfide elastic stress luminescent material Sr1-xZn2-yS2O:Ax,By。
8. The method according to claim 7, wherein in step 1), said Sr is derived from carbonate thereof; the rare earth ions adopt oxides thereof as raw materials; mn is obtained from carbonate.
9. The method of claim 7, wherein in the step 2), the protective atmosphere is pure argon atmosphere or pure nitrogen atmosphere.
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CN110628423B (en) * 2019-10-09 2020-11-20 厦门大学 Oxysulfide elastic stress luminescent material and preparation method thereof
CN112340712B (en) * 2020-11-09 2022-07-01 厦门大学 Nitrogen oxide elastic stress luminescent material and preparation method thereof
CN113214823B (en) * 2021-05-21 2022-06-17 山东大学 Ternary metal oxysulfide with long afterglow and mechanoluminescence and preparation method thereof
CN113563078A (en) * 2021-07-29 2021-10-29 南京理工大学 Trivalent bismuth ion enhanced manganese doped SrZn2S2O-oxysulfide scintillator and method for producing same

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