CN110628423B - A kind of oxysulfide elastic stress luminescent material and preparation method thereof - Google Patents

Abstract

An oxysulfide elastic stress luminescent material and a preparation method thereof belong to the field of inorganic luminescent materials. The general chemical expression of the oxysulfide elastic stress luminescent material is Sr _1-x Zn _{2- y} S ₂ O:A _x , By , wherein 0≤x≤1, 0≤y≤2, x and _y Indicates molar percentage, 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, etc.; B It is at least one of transition metal ions Mn or Cu. Preparation: The raw materials of each metal element are weighed according to their stoichiometric ratio, ground and mixed uniformly in an agate bowl, and the mixed powder is placed in an alumina crucible, heated to 800-1200 ℃ in a protective atmosphere or vacuum, and kept for 10-48 hours. , naturally cooled to room temperature with the furnace; the cooled powder is ground to obtain the oxysulfide elastic stress luminescent material.

Description

A kind of oxysulfide elastic stress luminescent material and preparation method thereof

technical field

The invention belongs to the field of inorganic light-emitting materials, in particular to an oxysulfide elastic stress light-emitting material and a preparation method thereof.

Background technique

Mechanoluminescence (ML) materials refer to solid materials that emit light under the action of various mechanical forces (such as extrusion, friction, impact, stretching, and twisting). According to the degree of deformation of the material and whether it can be recovered, stress luminescent materials are divided into destructive fracture stress luminescent materials and non-destructive deformation stress luminescent materials, and non-destructive deformation stress luminescent materials can be divided into elastic stress luminescent materials and plastic stress luminescent materials. . Among them, elastic stress luminescence has the advantages of repeatability, luminous intensity proportional to stress, and high sensitivity. It has great application potential in the fields of building structure flaw detection, electronic signature system, electronic skin and so on.

Since Bacon et al. occasionally discovered the peculiar phenomenon of stress luminescence when they cut sugar cubes with a knife in 1605, material researchers have carried out a lot of work on the composition, structure, mechanism and application of stress luminescence materials. Lots 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 materials is extremely weak, which cannot be applied in practical production and life. The applied stress luminescent materials are all elastic stress luminescent materials, the types are limited to the following: SrAl ₂ O ₄ :Eu (green light), ZnS:Mn (yellow light); ZnS:Cu (blue-green light), CaZnOS : Mn (red light), etc. At present, the research on elastic stress luminescent materials mainly has the following problems: (1) There are few types of elastic stress luminescent materials with recoverability; (2) The known elastic stress luminescent materials have many luminous intensities, which are difficult to achieve application. (3) The mechanism of the stress luminescent material is still unclear, and the development and design of the stress luminescent material is relatively difficult.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide an oxysulfide elastic stress luminescent material and a preparation method thereof in view of the above deficiencies in the prior art.

The general chemical expression of the oxysulfide elastic stress luminescent material is Sr _1-x Zn _2-y S ₂ O:A _x , By , where 0≤x≤1, 0≤y≤2, x and _y Indicates molar percentage, 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, etc.; B It is at least one of transition metal ions Mn or Cu.

Preferably, the composition of the oxysulfide elastic stress luminescent material is 0≤x≤0.05, 0≤y≤0.1, and x and y are not zero at the same time.

The crystal structure of the oxysulfide elastic stress light-emitting material belongs to the orthorhombic system.

The oxysulfide elastic stress luminescent material does not need to be irradiated with ultraviolet light or visible light in advance, and stress luminescence can be produced by directly applying stress to the oxysulfide elastic stress luminescent material.

The oxysulfide elastic stress luminescent material does not need to be irradiated with ultraviolet light or visible light in advance, and stress is applied to its powder, or to the film or cylinder obtained by mixing the powder with the elastic polymer material. Stress luminescence occurs within the elastic limit.

The stress applied to the oxysulfide elastic stress luminescent material includes, but is not limited to, mechanical action such as friction, compression, tension, compression, impact, torsion, and ultrasound.

The stress luminescence intensity of the oxysulfide elastic stress luminescent material has a linear relationship with the applied stress.

A preparation method of an oxysulfide elastic stress luminescent material, comprising the following steps:

1) Sr adopts its oxide, hydroxide or carbonate as raw material, Zn adopts its sulfide as raw material, rare earth ion adopts its oxide, fluoride, nitrate or carbonate as raw material, and transition metal ion adopts its Oxides, nitrates and carbonates are used as raw materials, and each metal element is weighed according to its stoichiometric ratio, ground and mixed in an agate bowl to obtain mixed powder;

2) placing the ground mixed powder in step 1) in an alumina crucible, heating up to 800-1200° C. in a protective atmosphere or in a vacuum, keeping the temperature for 10-48 hours, and naturally cooling to room temperature with the furnace;

3) grinding the cooled powder in step 2) to obtain the oxysulfide elastic stress luminescent material Sr _1-x Zn _2-y S ₂ O:A _x , _By .

In step 1), preferably, the Sr adopts its carbonate as a raw material; the rare earth ion adopts its oxide as a raw material; the Mn adopts its carbonate as a raw material; and the Cu adopts its sulfide as a raw material. raw material.

In step 2), the protective atmosphere is a pure argon atmosphere or a pure nitrogen atmosphere.

Compared with the prior art, the present invention has the following advantages and gains:

1) The present invention is prepared by a traditional solid-phase reaction method, and the process is simple, the equipment requirements are low, the conditions are easy to control, the cost is low, no toxic and harmful substances are produced in the preparation process, and the environment is friendly.

2) The oxysulfide elastic stress luminescent material prepared by the present invention can realize stress luminescence with adjustable luminescence by doping with different rare earth ions or transition metal ions.

3) The oxysulfide elastic stress luminescent material prepared by the present invention has a proportional relationship between the stress luminescence intensity and the applied stress within a certain elastic range, and can be applied to the detection of stress distribution.

Description of drawings

Fig. 1 is the X-ray diffraction spectrum of the sample powders prepared in Examples 1-3 of the present invention.

FIG. 2 is the emission spectrum of the samples prepared in Examples 1-3 of the present invention.

FIG. 3 is the rubbing spectrum of the samples prepared in Examples 1-3 of the present invention.

FIG. 4 is a fitting curve of the relationship between the stress luminescence intensity and the pressure of the sample prepared in Example 1 of the present invention.

Detailed ways

The following embodiments will further illustrate the present invention in detail with reference to the accompanying drawings, but the embodiments of the present invention are not limited thereto.

Embodiments 1 to 3:

Select strontium carbonate, zinc sulfide and transition metal carbonate or rare earth ion oxide as raw materials, take by weighing raw materials (specifically as shown in Table 1) according to the molar ratio of each element, put above-mentioned raw materials into an agate mortar and grind, mix homogeneously Then, take an appropriate amount of sample and put it into a corundum crucible, then put the crucible into the corundum boat, push the corundum boat into the tube furnace, and heat it up to 1000 °C for 24 hours under the protective atmosphere of pure argon. Cool naturally. The cooled sample is ground for 10 to 30 minutes to obtain an oxygen-sulfur compound-based stress luminescent powder.

Table 1 Sample ratios of Examples 1 to 3

X射线衍射分析表明样品在1000℃下煅烧24h可以得到SrZn₂S₂O纯相，属于斜方晶系，过渡金属Mn或稀土离子Pr、Yb的掺杂没有影响晶相的形成，且没有观察到其他杂相。Fig. 1 is the X-ray diffraction pattern of the samples prepared in Examples 1 to 3, the spectral line is measured by Bruker d8-advance Bruker X-ray diffractometer, the test voltage is 40kv, the test current is 40mA, and Cu-Kα rays are selected for use, and the wavelength is

X-ray diffraction analysis showed that the pure phase of SrZn ₂ S ₂ O could be obtained by calcining the sample at 1000 °C for 24 hours, which belonged to the orthorhombic system. The doping of transition metal Mn or rare earth ions Pr and Yb did not affect the formation of the crystal phase, and no observation to other miscellaneous phases.

Figure 2 shows the emission spectra of the samples prepared in Examples 1 to 3, which were measured by Edinburgh Instruments FL980 steady-state and transient luminescence spectrometer. Under the excitation of 270 nm light, the sample SrZn _1.99 S ₂ O:Mn _0.01 in Example 1 exhibits yellow emission with a broad peak emission, and the emission peak is at 584 nm, originating from Mn ²⁺ electrons from ⁴ T ₁ ( ⁴ G) to ⁶ A ₁ ( ⁶ S) energy level transition. In Example 2, the sample Sr _0.99 Zn ₂ S ₂ O: Pr _0.01 presents a linear spectrum, in which the luminescence at 490 nm and 510 nm originates from the transition of Pr ³⁺ electrons from ³ P ₀ to ³ H ₄ and ³ H ₄ , and the luminescence at 670 nm originates from the transition of Pr 3+ electrons from 3 P 0 to 3 H 4 and 3 H 4 Pr ³⁺ electron transition from ³ P ₀ to ³ F ₂ . In Example 3, the sample Sr _0.99 Zn ₂ S ₂ O:Yb _0.01 exhibits linear near-infrared emission with an emission peak at 980 nm, which is attributed to the transition of Yb3+ electrons from ³ F _5/2 to ² F _7/2 .

Fig. 3 is the friction spectrum of the samples prepared in Examples 1-3. The sample powder was put into the agate bowl, and the sample was rubbed with a glass rod to emit light. At the same time, the ocean optical fiber spectrometer QE pro was used to collect the luminescence of the samples. The data acquisition and integration time was 1s. As shown in Fig. 3, the samples all exhibited stress luminescence, and their triboluminescence spectra and emission spectra were basically consistent.

4 is a fitting curve of the relationship between the stress luminescence intensity of the sample prepared in Example 1 and the pressure. Shimadzu AGS-X series electronic universal testing machine was used to conduct pressure luminescence experiments, the control force range was 0-1800N, and Hamamatsu photon detector C9692 was used to collect luminous intensity. Figure 4 was used to fit the luminous intensity and stress. The goodness R ² =0.9941, indicating that the two have a good linear relationship.

The invention discloses an oxysulfide elastic stress luminescent material Sr _1-x Zn _2-y S ₂ O:A _x , By , wherein 0≤x≤1, 0≤y≤2, x and _y represent mole percentages 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 transition metal One or both of the ions Mn or Cu. The present invention also discloses a method for preparing the above-mentioned oxysulfide elastic stress luminescent material: (1) weighing the raw materials according to the molar ratio of the elements; (2) grinding the raw materials weighed in step (1) evenly, placing them in an inert atmosphere or calcining under vacuum; (3) taking out the calcined sample and grinding to obtain the above-mentioned oxysulfide elastic stress luminescent material. The elastic stress material of the invention has adjustable luminescence wavelength band, high luminescence efficiency and simple preparation method, and has potential application value in application fields involving stress monitoring, such as structural damage detection, electronic signature system, electronic skin and the like.

Claims (9)

1. An oxysulfide elastic stress luminescent material is characterized in that the chemical expression general formula is Sr_1-xZn_2-yS₂O:A_x,B_yWherein 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 Sr_1-xZn_2-yS₂O:A_x,B_y。

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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