CN116042219B - 一种动态多模变色防伪材料及其制备方法 - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 230000005284 excitation Effects 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000005424 photoluminescence Methods 0.000 claims abstract 2
- 239000002994 raw material Substances 0.000 claims description 11
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004020 luminiscence type Methods 0.000 claims description 3
- 230000000638 stimulation Effects 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000009423 ventilation Methods 0.000 claims 1
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005273 aeration Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000001443 photoexcitation Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
本发明公开了一种动态多模变色防伪材料及其制备方法,涉及变色防伪技术领域。该变色防伪材料的化学组成式为LiGa1‑xCexO2,其中,x为0.008~0.02。本发明还公开了上述变色防伪材料的制备方法,其通过高温固相法进行制备,所制备的防伪材料在紫外光激发下,可产生橘黄色的光致发光,在关闭激发源后,产生动态的余辉(橘黄色→白色),当使用650nm的滤波片时,可观察到近红外余辉,继而将样品用254nm紫外光进行预照射后,搁置一段时间,然后使用980nm的近红外激光器照射时,可产生光激励余辉。与现有的荧光防伪材料相比,具有防伪模式多样化,发光颜色鲜艳,制备方法简单,且其防伪特性难以被模仿,具有更广泛的应用价值。
Description
技术领域
本发明属于动态多模变色防伪领域;涉及该动态多模变色防伪材料的制备方法;本发明同时还涉及该动态多模变色材料在防伪领域中的应用,属于化学制备领域和防伪技术领域。
背景技术
当前,伪造已经成为全球面临的一个严重性问题,根据相关资料显示,全球假冒伪劣产品的年产总值已超过5000亿美元,国内市场年产总值也达到了1000多亿人民币。为了有效打击假冒伪劣商品,各种防伪技术手段包括数字水印、二维码、全息定位烫印、化学油墨、条形码和荧光等防伪技术,已经成为保护正规合法产品的一把利剑。其中,基于镧系掺杂无机荧光材料的防伪策略以其隐蔽性好、仿造难、重现性强、色彩鲜艳、成本低等优点引起了人们的广泛关注。
但现阶段镧系掺杂无机荧光材料主要通过单模降频方式来实现的,容易被伪造。相比于传统的单色静态发光材料,动态多模发光材料能够在同一材料中实现多种发光模式,此类发光材料由于发光颜色可调、不易仿制、编码容量大、保密性高,大大增加了造假的难度,在防伪领域中具有很高的实用价值。可以极大地提高防伪级别。因此,如何制备一种动态多模的防伪材料成为一个重要的研究课题。
发明内容
鉴于现有荧光防伪技术的不足,本发明旨在于提供一种动态多模变色防伪材料及其制备方法,该防伪材料具有在紫外光、外力刺激以及近红外光激发下产生动态余辉变色、机械发光以及光激励余辉的功能。
所述动态多模变色防伪材料是在254nm紫外光激发下,产生动态的可见光余辉和静态的近红外余辉;在外力刺激下,产生近红外力致发光;在980nm的近红外光激发下,产生光激励余辉。
一、LiGa1-xCexO2的制备
本发明LiGa1-xCexO2防伪材料的制备,其包括如下步骤:
S1、以Li2CO3,Ga2O3和CeO2为原料,按照LiGa1-xCexO2化学组成式中的Li、Ga和Ce的化学计量比,称取上述相应原料并混合,在玛瑙中研磨均匀;
S2、在管式炉中,将通气流量(V(H2):V(N2)=1:9)设置为18ml,升温至1300℃进行烧结,保温时间6h;
S3、将步骤S2中所得的物料降至室温后研磨,可制得动态多模变色防伪材料。
本发明的防伪材料具有隐蔽性好、仿造难、重现性强、色彩鲜艳、成本低等优点,该防伪材料可以在紫外光和近红外光激发下产生肉眼可辨的颜色变化,具有制备方法简单、发光模式多样化、编码容量大以及保密性高等优点。同时,该防伪材料的化学性质稳定,其应用面更广,如可涂写于货币、发票、证书、印章以及各类商品标签上等,起到很好的荧光防伪的作用,具有更广泛更实用的价值。
附图说明
图1为本发明实施例1、2为所制备的防伪材料的XRD图谱。
图2为实施例1、2所制备的防伪材料在254nm紫外光激发下的光致发光光谱图。
图3为实施例2所制备的防伪材料在254nm紫外光预照射后在不同时间段的980nm近红外光源激发下的光激励光谱图。
图4为实施例2所制备的防伪材料在外力刺激下的力致发光光谱图。
图5为实施例2所制备的防伪材料在254nm紫外光激发下的余辉衰减图。
图6为实施例2所制备的防伪材料在980nm近红外光激发下的光激励余辉衰减图。
图7为实施例2所制备的防伪材料在254nm紫外光激发下的余辉光谱图。
图8为实施例2所制备的防伪材料在980nm近红外光激发下的光激励光谱图。
具体实施方式
实施例1
以Li2CO3,Ga2O3为原料,按照化学组成式LiGaO2中的Li和Ga的化学计量比,称取上述相应原料并混合。然后,将上述混和均匀的原料放入管式炉中,将通气流量(V(H2):V(N2)=1:9)设置为18ml,升温至1300℃进行烧结,保温时间6h。最后,降至室温进行研磨,即制得LiGaO2防伪材料,由实施例1所制得的防伪材料的XRD图谱见图1,从图1可以看出,未出现杂相,具有较好的结晶性,形成了良好的单相。
实施例2
以Li2CO3,Ga2O3和CeO2为原料,按照化学组成式LiGa0.984Ce0.016O2中的Li、Ga和Ce的化学计量比,称取上述相应原料并混合。然后,将上述混和均匀的原料放入管式炉中,将通气流量(V(H2):V(N2)=1:9)设置为18ml,升温至1300℃进行烧结,保温时间6h。最后,降至室温进行研磨,即制得LiGa0.984Ce0.016O2防伪材料,由实施例2所制得的防伪材料的XRD图谱见图1,从图1可以看出,未出现杂相,具有较好的结晶性,形成了良好的单相。
由实施例1、2所制得的防伪材料在紫外光激发下的光谱图见图2,可观察到其发光波长涵盖了可见光区和近红外光区。
Claims (6)
1.一种动态多模变色防伪材料,其化学组成式为LiGa1-xCexO2,其中,x为0.008~0.02。
2.如权利要求1所述的动态多模变色防伪材料,其特征在于:x=0.016。
3.如权利要求1所述动态多模变色防伪材料的合成方法,是以Li2CO3,Ga2O3和CeO2为原料,按照化学组成式LiGa0.984Ce0.016O2中的Li、Ga和Ce的化学计量比,称取上述原料并混合,然后,将上述混合均匀的原料转移到氧化铝坩埚中,并放入通气流量为18ml的管式炉中,其中V(H2):V(N2)为1:9,升温至1300℃进行煅烧,保温时间6h,最后降至室温后,将样品取出,进行研磨,即得动态多模变色防伪材料。
4.如权利要求1所述动态多模变色防伪材料,其特征在于:在254nm紫外光激发下,可产生橙黄色光致发光,关闭紫外光源后,产生动态余辉,所述动态余辉为橙黄色→白色,继而在关闭紫外光源后,使用650nm的滤波片时,观察到近红外余辉。
5.如权利要求1所述动态多模变色防伪材料,其特征在于:在外力刺激下,可产生近红外力致发光。
6.如权利要求1所述动态多模变色防伪材料,其特征在于:在254nm紫外光预照射后,搁置一段时间,然后在980nm的近红外激光器照射下,可产生橙黄色光激励余辉。
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JP2005213421A (ja) * | 2004-01-30 | 2005-08-11 | Sony Corp | 発光性複合材料 |
JP2011190386A (ja) * | 2010-03-16 | 2011-09-29 | Tohoku Univ | 中性子シンチレータ用酸化物結晶及び中性子検出器 |
CN113201338A (zh) * | 2021-03-18 | 2021-08-03 | 兰州大学 | 一种多模态发光防伪材料及其制备方法和应用 |
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JP2005213421A (ja) * | 2004-01-30 | 2005-08-11 | Sony Corp | 発光性複合材料 |
JP2011190386A (ja) * | 2010-03-16 | 2011-09-29 | Tohoku Univ | 中性子シンチレータ用酸化物結晶及び中性子検出器 |
CN113201338A (zh) * | 2021-03-18 | 2021-08-03 | 兰州大学 | 一种多模态发光防伪材料及其制备方法和应用 |
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"A comparative investigation of Ce3+/Dy3+ and Eu2+ doped LiAlO2 phosphors for high dose radiation dosimetry: Explanation of defect recombination mechanism using PL, TL and EPR study";Karan Kumar Gupta et al.;Journal of Luminescence;第188卷;第81-95页 * |
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