WO2020186767A1 - Composite-phase mechanoluminescent materials with adjustable color and intensity, and preparation method thereof - Google Patents

Composite-phase mechanoluminescent materials with adjustable color and intensity, and preparation method thereof Download PDF

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Publication number
WO2020186767A1
WO2020186767A1 PCT/CN2019/114684 CN2019114684W WO2020186767A1 WO 2020186767 A1 WO2020186767 A1 WO 2020186767A1 CN 2019114684 W CN2019114684 W CN 2019114684W WO 2020186767 A1 WO2020186767 A1 WO 2020186767A1
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composite
intensity
phase
mechanoluminescent
adjustable color
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PCT/CN2019/114684
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English (en)
French (fr)
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Dengfeng PENG
Yue Jiang
Zhongjin XIE
Shaohui MAO
Sicen QU
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Shenzhen University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/57—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing manganese or rhenium
    • C09K11/572—Chalcogenides
    • C09K11/576—Chalcogenides with alkaline earth metals

Definitions

  • the present invention belongs to the technical field of mechanoluminescent functional materials, and relates to a composite-phase mechanoluminescent material with adjustable color and intensity, and a preparation method thereof.
  • Mechanoluminescence is dynamic light emission resulting from any mechanical action (such as twisting, pressing, stretching, breaking, etc. ) on a solid material. Unlike the excitation modes of common photoluminescence and electroluminescence, the mechanoluminescence is direct light emission resulting from a mechanical stress, requiring no energization or illumination. Moreover, within a certain elasticity range, the intensity is linearly related to the mechanical stress.
  • the prepared devices have characteristics of wireless transmission, non-destruction, repeatability, real-time visualization and the like.
  • intelligent mechanoluminescent materials become a hot research field at present, and have great application prospect in fields such as artificial intelligence, paperless office, intelligent anti-counterfeiting, stress sensing, touch screen technology and electronic skin.
  • intelligent mechanoluminescent materials Under a weak external force, intelligent mechanoluminescent materials exhibit MLcharacteristics visible to the naked eyes. Within a certain stress range, the light emission of an object resulting from an external force is called elastic ML, and this ML is non-destructive and self-restorative. Due to the characteristic that the non-destructive luminescence and the ML intensity of the elastic mechanoluminescent materials are directly proportional to the applied mechanical stress, the elastic mechanoluminescent materials can be applied in the preparation of intelligent stress distribution sensors to realize real-time stress distribution visualization for an object to be detected. The elastic ML materials also have considerable advantages in artificial intelligence, bridge stress detection, earthquake prediction, electronic skin and intelligent anti-counterfeiting systems. So far, there have been dozens of elastic ML material systems.
  • the already reported ML materials show low non-destructive ML intensity, low luminous efficiency (below 1%in most cases) , and low repeatability, and thus cannot meet the production requirements.
  • the present invention provides a diphaêto-structure ML material with simple operation, low cost, and adjustable color and intensity.
  • an objective of the present invention is to provide a composite-phase mechanoluminescent material with adjustable color and intensity.
  • the material is high in elastic mechanoluminescenceintensity, simple in preparation process, low in cost and stable in chemical properties, and can directly respond to mechanical stress signals in various forms (e.g., compression, stretching, bending, collision, rubbing, twisting, etc. ) . Light emitted by the material can be observed with the naked eyes in a dark environment.
  • the chemical formula of the composite-phase mechanoluminescent material with adjustable color and intensity in the present invention is ZnS-AOZnS: xN, yM (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1) , where N is a substitution element at the Zn-site and is one or more of Cu, Mn and Cr, M is a substitution element at the A-site and is one or more of Pr, Tb, Sm, Ho, Nd, Bi, Pb, Ag, Ti, Gd, Eu and Yb, A is one or more of Ca, Sr and Ba, and x and y represent molar percentages.
  • a method for preparing the composite-phase mechanoluminescent material with adjustable color and intensity in the present invention includes the following steps:
  • the prepared mechanoluminescent powder which is already grinded and sieved, is formed as a composite together with an optical transparent organic high-molecular elastic material, preferably PET, TPU or PDMS; the composite is machined into sheets or coated on the surface of a component to be measured; and, the mechanical stress applied onto the composite or component can be transformed into optical signals which are then transmitted, so that the stress-light direct energy conversion with adjustable color and intensity is realized. Moreover, within a certain elasticity range, the intensity is directly proportional to the applied stress, and the change in light brightness can be observed with the naked eyes.
  • an optical transparent organic high-molecular elastic material preferably PET, TPU or PDMS
  • the composite-phase mechanoluminescent material of the present invention is mixed with PDMS and then machined into sheets. Under a certain stress, the mechanoluminescence color of samples changes and the mechanoluminescence peak is red-shifted.
  • the intensity of the samples is enhanced, and the intensity can be observed in a bright environment.
  • the composite-phase mechanoluminescent material is synthesized in a single step, the preparation process is simple, the cost is low, and the presence of impurity phases during the preparation is reduced. Accordingly, the composite-phase mechanoluminescent material with excellent light emission characteristics is synthesized.
  • Fig. 1 is an X-ray diffraction pattern of a composite-phase mechanoluminescent material according to Embodiment 1 of the present invention.
  • Fig. 2 is a photoluminescence (PL) spectrum of the composite-phase mechanoluminescent material product according to Embodiment 1 of the present invention.
  • Fig. 3 is a mechanoluminescence (ML) spectrum of the composite-phase mechanoluminescent material product according to Embodiment 1 of the present invention.
  • Fig. 4 is a mechanoluminescence (ML) spectrum of a composite-phase mechanoluminescent material according to Embodiment 2 of the present invention.
  • Fig. 5 is a mechanoluminescence (ML) spectrumintegratedintensity over 500 ⁇ 750 nm of the composite-phase mechanoluminescent material product under mechanical excitation at 35N as a function of CaZnOS/ZnS molar ratio in the precursoraccording to Embodiment 1 of the present invention.
  • ML mechanoluminescence
  • the mixed raw materials at the above ratio were put into an agate mortar, then added with absolute ethyl alcohol or deionized water, and grinded and uniformly mixed in the agate mortar.
  • the mixture was dried in an oven at 100°C to obtain mixed powder.
  • the uniformly grinded powder was put into an alumina crucible, then heated to 800°C to 1400°Cat a rate of 1°C/min to 100°C/min in an inert atmosphere, calcined for 0.5h to 24h, and naturally cooled.
  • the cooled powder was finely grinded, and then sieved with a 300-mesh sieve to obtain composite-phase mechanoluminescent material ZnS-CaZnOS: Mn powder.
  • the obtained mechanoluminescent powder was formed as a composite with an optical transparent organic high-molecular elastic material (PET, TPU or PDMS) , and a device was prepared from the composite to test the mechanoluminescence characteristic.
  • Raw materials are prepared: CaCO 3 , ZnS, MnCO 3 , Pr (NO 3 ) 3 -6H 2 O and LiF are used as raw materials, wherein oxides or carbonates of CaCO 3 , sulfides of Zn and S, and oxides, carbonates or soluble nitrates, sulfates or chlorides of Mn and Pr were used as raw materials. A cosolvent LiF was added. The raw materials were weighed according to stoichiometric ratios. A proper amount of absolute ethyl alcohol or deionized water was then added in the mixed raw materials, and the mixture was grinded and uniformly mixed in an agate mortar and then dried in an oven at 100°Cto obtain mixed powder.
  • the cooled powder obtained in the step b) was grinded for 10 min to 30 min, and then sieved with a 300-mesh sieve to obtain composite-phase mechanoluminescent material ZnS-CaZnOS: Mn powder.
  • the obtained mechanoluminescent powder was formed as a composite with an optical transparent organic high-molecular elastic material (PET, TPU or PDMS) , and a device was prepared from the composite to test the mechanoluminescence characteristic.
  • PET optical transparent organic high-molecular elastic material
  • Raw materials are prepared: BaCO 3 , ZnS, MnCO 3 , Pr (NO 3 ) 3 -6H 2 O and LiF were used as raw materials, wherein oxides or carbonates of BaCO 3 , sulfides of Zn and S, and oxides, carbonates or soluble nitrates, sulfates or chlorides of Mn and Pr were used as raw materials. A cosolvent LiF was added. The raw materials were weighed according to stoichiometric ratios. A proper amount of absolute ethyl alcohol or deionized water was then added in the mixed raw materials, and the mixture was grinded and uniformly mixed in an agate mortar and then dried in an oven at 100°Cto obtain mixed powder.
  • the cooled powder obtained in the step b) was grinded for 10 min to 30 min, and then sieved with a 300-mesh sieve to obtain composite-phase mechanoluminescent material ZnS-BaZnOS: Mn powder.
  • the obtained mechanoluminescent powder was formed as a composite with an optical transparent organic high-molecular elastic material (PET, TPU or PDMS) , and a device was prepared from the composite to test the mechanoluminescence characteristic.
  • PET optical transparent organic high-molecular elastic material
  • Raw materials are prepared: SrCO 3 , ZnS, MnCO 3 , Pr (NO 3 ) 3 -6H 2 O and LiF were used as raw materials, wherein oxides or carbonates of SrCO 3 , sulfides of Zn and S, and oxides, carbonates or soluble nitrates, sulfates or chlorides of Mn and Pr were used as raw materials. A cosolvent LiF was added. The raw materials were weighed according to stoichiometric ratios. A proper amount of absolute ethyl alcohol or deionized water was then added in the mixed raw materials, and the mixture was grinded and uniformly mixed in an agate mortar and then dried in an oven at 100°C to obtain mixed powder.
  • the cooled powder obtained in the step b) was grinded for 10 min to 30 min, and then sieved with a 300-mesh sieve to obtain composite-phase mechanoluminescent material ZnS-SrZnOS: Mn powder.
  • the obtained mechanoluminescent powder was formed as a composite with an optical transparent organic high-molecular elastic material (PET, TPU or PDMS) , and a device was prepared from the composite to test the mechanoluminescence characteristic.
  • PET optical transparent organic high-molecular elastic material

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)
PCT/CN2019/114684 2019-03-18 2019-10-31 Composite-phase mechanoluminescent materials with adjustable color and intensity, and preparation method thereof WO2020186767A1 (en)

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CN116574505A (zh) * 2023-04-27 2023-08-11 桂林电子科技大学 一种镓酸盐应力发光材料的制备方法

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CN110223596B (zh) * 2019-07-09 2022-02-22 深圳大学 基于应力发光的防伪标签
CN111909689B (zh) * 2020-07-15 2023-02-28 深圳大学 力致发光复合材料及其制备方法和应用
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CN113214823B (zh) * 2021-05-21 2022-06-17 山东大学 一种兼有长余辉和力致发光的三元金属硫氧化物及其制备方法
CN114085668B (zh) * 2021-11-22 2023-07-18 厦门理工学院 一种硫氧化物弹性应力发光材料及其制备
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CN116574505A (zh) * 2023-04-27 2023-08-11 桂林电子科技大学 一种镓酸盐应力发光材料的制备方法

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