CN114456798A - 一种应力发光材料及其制备和应用 - Google Patents
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Abstract
本发明涉及一种应力发光材料及其制备和应用,组合物包括:应力发光材料、纳米粒子、弹性聚合物。本发明对机械力刺激具有灵敏的可视化响应,在无外部供电的情况下实现了力‑光的可视化传感,并增加了服装的装饰美观性。在柔性可穿戴传感、医疗健康监测、智慧交通警示等方面具有广泛的应用。
Description
技术领域
本发明属于应力发光技术领域,特别涉及一种应力发光材料及其制备和应用。
背景技术
近年来,随着新型高性能应力发光材料的不断发现,这些能够将机械能转化为光能的应力发光材料创造了解决现实问题的机会。在应力传感和成像、结构损伤监测、可穿戴照明设备、自供电显示器、机械能收集和转换方面的潜在应用而受到越来越多的关注。这些成果加快了应力发光的实用化进程并推动应力发光研究走向新的高度。弹性材料应力发光现象可以通过应用循环机械载荷而不断产生。掺杂激活剂的无机晶体由于其高机械强度和光学稳定性而被认为在弹性应力发光方面具有非常大的潜力。应力发光材料在可穿戴集成等方面的应用取得了一定的进展,但在服用化上仍面临着一些问题:(1)目前弹性应力发光材料由于弹性基体的缓冲作用会消耗大量机械能从而导致作用在发光粉颗粒上的应力较弱;(2)应力发光粉自身结构问题导致其发光性能较差;(3)聚合物薄膜基底致密的结构与现有服装织物的结构不相容,导致贴合性存在问题;(4)许多应力发光材料制备工艺繁琐,成本较高,难以达到规模化连续生产。因此如何制备出具备较好发光性能、成本低廉、工艺操作简单的应力发光智能织物成为当前研究的热点。
发明内容
本发明所要解决的技术问题是提供一种应力发光材料及其制备和应用,克服现有应力发光织物发光性能较差,且不能连续制备的缺陷,该应力发光智能织物发光性能较好,工艺流程简单,适合大批量生产。
本发明提供一种应力发光材料组合物,组合物包括:应力发光粉、纳米粒子、弹性聚合物;其中纳米粒子掺杂含量为应力发光粉的0-30wt%;应力发光粉掺杂含量为弹性聚合物的20-100wt%。
所述纳米粒子为氧化铝或/二氧化硅纳米粒子,粒径为10~250nm,优选10~50nm;
优选地,所述纳米粒子掺杂含量为应力发光粉的10-20wt%。
所述弹性聚合物为硅胶和/或聚二甲基硅氧烷;所述应力发光材料为表面包覆氧化铝的掺杂铜元素的硫化锌颗粒、掺杂铜元素的硫化锌颗粒中的至少一种。
所述应力发光材料选用掺杂铜元素的硫化锌颗粒,通过高温固相法烧制。
所述应力发光材料由下列方法制备,包括:
(1)将硫化锌、激活剂、助熔剂混匀,烘干,煅烧,反应结束后取出并置于室温下冷却,然后洗涤,干燥,得到发光粉;
(2)采用非均匀成核法进行包覆:
将硫酸铝溶液滴加入发光粉体系中,滴加完毕后,60~80℃下反应1-2h,然后调节体系至中性,洗涤,干燥,煅烧,得到应力发光材料。
上述制备方法的优选方式如下:
所述步骤(1)中激活剂为硫酸铜、氯化铜、溴化铜中的一种或多种;助熔剂为氯化钠和氯化镁;
所述激活剂中Cu离子浓度为0.1-0.15mol%;氯化钠含量为硫化锌的4-8wt%;氯化镁含量为硫化锌的8-12wt%。
所述步骤(1)中烘干温度为100~120℃,时间5~8h;所述煅烧为1050~1150℃,时间2~4h;干燥温度为60~100℃,时间4~6h。
进一步地,步骤(1)中煅烧为烧粉温度需要控制在1050~1150℃,温度稳定后将粉体快速置入炉体内部并保持密闭状态反应2~4h;反应结束后快速取出粉体并置于室温下冷却。骤升骤降操作以保证粉体中压电相的含量。
所述步骤(1)中洗涤为用煮沸的去离子水浸泡并洗涤粉体,重复4~6次。
所述步骤(2)中硫酸铝溶液的浓度为0.1M~0.3M;发光粉体系为发光粉与缓冲液或水组成的混合体系;其中硫酸铝转化为氧化铝,氧化铝含量约为硫化锌的5-15wt%;
所述步骤(2)中滴速为5~7ml/min;干燥为60~100℃干燥2~4h;煅烧200~400℃下煅烧2~4h。
进一步,所述步骤(2)中采用非均匀成核法进行包覆,包覆材料为硫酸铝溶液,其浓度控制在0.1M~0.3M,将上述溶液缓慢滴入发光粉与缓冲液或去离子水组成的混合体系中,滴速控制在5~7ml/min;滴加完毕后,混合体系反应1~2h,温度控制在60~80℃;反应结束后用0.5M氢氧化钠溶液将混合体系调节至中性;洗涤3~5次,进行干燥,干燥条件为温度60~100℃,时间2~4h;干燥后置于200~400℃马弗炉内煅烧2~4h可得到表面包覆氧化铝的应力发光粉。
本发明的一种应力发光织物,表面涂覆所述应力发光材料组合物的弹性织物。
进一步地,将上述应力发光材料组合物通过丝网印刷方式涂敷于弹性织物表面,并进行热固化处理;热固化温度控制为60~150℃,热固化时间为5~30min。弹性织物可选用棉、锦纶、氨纶、聚酯纤维、棉仿面料。
本发明的一种应力发光纤维,所述应力发光纤维表面包覆所述应力发光材料组合物。
本发明提供一种应力发光纤维的制备方法,包括:
弹性纤维表面包覆所述应力发光材料组合物,150~220℃固化,得到应力发光纤维。
所述弹性纤维选用硅胶丝,直径为0.8~1.8mm。
所述应力发光纤维的连续化制备具体为:
将所述应力发光材料组合物进行预固化及脱泡处理,固化温度为60~80℃,固化时间5~10min;注入弹性纤维通过传送设备,依次通过包覆模具进行涂覆,加热装置进行加热固化,所述应力发光纤维制备过程中纤维的传送速度为0.8~5m/min;包覆模具的孔径为1~2mm;加热固化温度为150~220℃。
所述制备弹性应力发光纤维的连续化设备包括:纤维传送装置,溶液涂覆模具,加热装置,挤出机,冷却槽,收集装置等。所得到的应力发光纤维通过编织及缝合与织物相结合。弹性织物可选用棉、锦纶、氨纶、聚酯纤维、棉仿面料。
进一步,所述连续化设备依次包括:定滑轮1,包覆模具2,隧道窑3,动滑轮4。具体操作如下:将初始弹性纤维线卷固定在滑轮1上,牵伸一侧纤维依次通过注有应力发光浆料的包覆模具进行包覆、隧道窑进行加热固化,随后通过滑轮4对包覆好的纤维进行收线。
本发明的一种所述应力发光纤维在智能织物领域中的应用。
本发明所述发光织物在外力作用下能重复发光,响应速度快。通过隧道窑挤出设备在弹性纱线表面包覆应力发光复合涂层,热固化成型,可实现应力发光纤维批量制备与连续编织;通过丝网印刷技术将应力发光复合浆料印刷于织物表面,可实现发光织物的图案化。本发明对机械力刺激具有灵敏的可视化响应,在无外部供电的情况下实现了力-光的可视化传感,并增加了服装的装饰美观性。在柔性可穿戴传感、医疗健康监测、智慧交通警示等方面具有广泛的应用。
有益效果
本发明所述的应力发光织物,在各种应力作用,不限于拉力、摩擦、压力等,可在较明亮光线环境中观察到发光效果。本发明通过以下几种方法提高应力发光效果:①采用高温固相方法制备出压电相粉体;②粉体表面包覆氧化铝;③在复合体系中添加氧化铝或二氧化硅纳米粒子。
本发明的制备方法简单,通过自搭设备实现了应力发光纤维百米以上的连续化制备;通过丝网印刷工艺可实现大批量生产。本发明可使应力发光材料得到大规模生产,提升其实际应用价值,在智能服装领域有良好的应用前景。
本发明中制备一种高性能应力发光纤维的连续化制备及其应用的研究主要包括以下几个方面:①调配硫化锌颗粒与掺杂剂的比例,调控高温烧制条件(如烧结温度、保温时间调控),对粉体进行表面包覆提升应力发光效果;②合理调配应力发光粉、氧化铝或二氧化硅纳米粒子与弹性聚合物比例,增强发光效果;③采用连续化制备方法,可成功制备上百米应力发光纤维,实现应力发光纤维的长程构筑;④弹性应力发光薄膜可多次丝网印刷于弹性织物上,工艺流程操作简单,适合大批量生产。
本专利在此研究基础上对粉体表面进行包覆,其应力发光效果更佳(如图所示6)。
附图说明
图1实施例1制备的应力发光粉显微形貌照片;
图2实施例1应力发光浆料结构示意图;其中1为ZnS:Cu应力发光粉,2为氧化铝纳米粒子,3为弹性聚合物基底;
图3实施例1制备的连续化应力发光纤维制备示意图:其中1为定滑轮,2为包覆模具,3为隧道窑,4为动滑轮;
图4实施例7中制备的应力发光纤维示意图:(a)应力发光纤维结构示意图;(b)应力发光纤维实物数码照片;
图5实施例7中应力发光纤维的应用:(a)应力发光纤维编织织物数码照片;(b)丝网印刷织物未拉伸与拉伸发光展示;(c)发光织物(背部)穿戴状态下演示发光;(d)发光织物(肘部)穿戴状态下演示发光;
图6两种晶型粉体以及分别实施包覆条件后粉体的对发光效果;
图7实施例1-3中在应力作用下使用硅胶基底材料的应力发光纤维的相对发光强度信号。
图8实施例4-6中在应力作用下使用聚二甲基硅氧烷基底材料的应力发光纤维的相对发光强度信号。
图9实施例7-9中在应力作用下使用混合胶料基底材料的应力发光纤维的相对发光强度信号。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
原料的来源及规格参数:
氧化铝、二氧化硅(苏州远特新材料有限公司,10nm);
硅胶(东莞市科多有机硅材料有限公司);
聚二甲基硅氧烷(美国陶氏)。
实施例1
(1)烧制应力发光粉
采用高温固相法烧制含铜元素硫化锌基应力发光粉。烧粉参数:称取硫化锌原料400g,添加剂包括:硫酸铜粉末0.656g,氯化钠固体24g,氯化镁固体40g,将添加剂溶解于200ml去离子水中,搅拌溶解;将添加剂溶液与硫化锌原料充分混合;放置烘箱内烘干,烘干条件为温度100℃,时间8h。烘干后,至于1100℃马弗炉中煅烧3h;反应结束后将粉体迅速取出,室温下冷却后使用高温去离子水将粉体进行清洗,将粉体浸泡于去离子水中30min后去除上层液体,重复5次去除多余杂质;清洗后放入烘箱内在100℃下干燥4h。得到未包覆的压电相应力发光粉,如图6所示。
取出干燥后的粉体,称取150g,放入300ml 0.5M氢氧化钠溶液中浸泡5h;水洗至中性后干燥;将预处理后的粉体与1500ml缓冲溶液混合,缓冲液pH约为5,搅拌30min;配置浓度为0.1M硫酸铝溶液,取750ml该溶液滴加入发光粉混合体系中,滴加速度为7ml/min;滴加完毕后,加热搅拌1h,加热温度为70℃;反应结束后,向反应体系中滴加氢氧化钠溶液,浓度为0.5M,调节pH为7;静置,洗涤,干燥。得到表面被包覆的的压电相粉体,如图6所示。
(2)制备弹性应力发光复合浆料
称取(1)中制备得到的ZnS:Cu应力发光粉10g,硅胶20g,将上述材料充分混合;置于真空烘箱内,进行预固化脱泡处理,温度为60℃,温度为5min,得到应力发光浆料,其结构如图2。
(3)制备应力发光纤维
将(2)中所述浆料置于真空烘箱内进行脱泡及预固化处理,温度设为60℃,时间10min,结束后将浆料倒入包覆模具中;采用自搭的纤维连续化制备装置(如图3所示),硅胶纤维(直径为1mm)通过辊轮传送设备,通过包覆模具进行涂覆,经高温固化后收集,得到应力发光纤维(如图4)。包覆模具孔径为1.2mm,纤维传输速度为3m/min,固化温度为200℃。将制备得到的应力发光纤维通过编织缝合于织物表面,构建应力发光智能织物。
(4)进一步构建应力发光织物
将(2)中所述浆料导入丝网印刷板内,印刷于弹性织物表面,在100℃条件下固化3min,弹性织物选用90%棉+10%聚酯纤维,得到应力发光智能织物。
实施例2
称取实施例1中制备的ZnS:Cu应力发光粉10g,10nm二氧化硅粒子3g,硅胶20g,将上述材料充分混合;置于真空烘箱内,进行预固化及脱泡处理,温度为60℃,温度为5min,得到应力发光浆料;按照实施例1中的步骤(3)与(4)制备应力发光织物。
实施例3
称取实施例1中制备的ZnS:Cu应力发光粉10g,10nm氧化铝粒子3g,硅胶20g,将上述材料充分混合;置于真空烘箱内,进行预固化及脱泡处理,温度为60℃,温度为5min,得到应力发光浆料;按照实施例1中的步骤(3)与(4)制备应力发光织物。
实施例4
称取实施例1中制备的ZnS:Cu应力发光粉10g,PDMS(聚二甲基硅氧烷)20g,将上述材料充分混合;置于真空烘箱内,进行预固化及脱泡处理,温度为60℃,温度为10min,得到应力发光浆料;按照实施例1中的步骤(3)与(4)制备应力发光织物。
实施例5
称取实施例1中制备的ZnS:Cu应力发光粉10g,10nm二氧化硅粒子3g,PDMS(聚二甲基硅氧烷)20g,将上述材料充分混合;置于真空烘箱内,进行预固化及脱泡处理,温度为60℃,温度为10min,得到应力发光浆料;按照实施例1中的步骤(3)与(4)制备应力发光织物。
实施例6
称取实施例1中制备的ZnS:Cu应力发光粉10g,10nm氧化铝粒子3g,PDMS(聚二甲基硅氧烷)20g,将上述材料充分混合;置于真空烘箱内,进行预固化及脱泡处理,温度为60℃,温度为10min,得到应力发光浆料;按照实施例1中的步骤(3)与(4)制备应力发光织物。
实施例7
称取实施例1中制备的ZnS:Cu应力发光粉10g,PDMS(聚二甲基硅氧烷)10g,硅胶10g,将上述材料充分混合;置于真空烘箱内,进行预固化及脱泡处理,温度为60℃,温度为10min,得到应力发光浆料;按照实施例1中的步骤(3)与(4)制备应力发光织物。
实施例8
称取实施例1中制备的ZnS:Cu应力发光粉10g,10nm二氧化硅粒子3g,PDMS(聚二甲基硅氧烷)10g,硅胶10g,将上述材料充分混合;置于真空烘箱内,进行预固化及脱泡处理,温度为60℃,温度为10min,得到应力发光浆料;按照实施例1中的步骤(3)与(4)制备应力发光织物。
实施例9
称取实施例1中制备的ZnS:Cu应力发光粉10g,10nm氧化铝粒子3g,PDMS(聚二甲基硅氧烷)10g,硅胶10g,将上述材料充分混合;置于真空烘箱内,进行预固化及脱泡处理,温度为60℃,温度为10min,得到应力发光浆料;按照实施例1中的步骤(3)与(4)制备应力发光织物。
本方法所体现的高性能应力发光效果:弹性应力发光浆料体系中,在聚合物基底中额外添加掺杂粒子的发光效果提升,其中掺杂氧化铝的效果比掺杂二氧化硅的效果更加;双组份聚合物基底的发光效果优于单组份聚合物基底。
本文专利主要是集中于弹性应力发光复合体发光性能的提升:通过提升发光粉自身性能,添加最佳比例掺杂粒子以及调配聚合物基底组分使得复合体发光效果得到提升;本文专利中弹性应力发光复合浆料主要使用硅胶基底材质,与传统单纯使用聚二甲基硅氧烷相比较,其与织物贴合效果更好,可适用于织物印花,应用更加广泛;本专利着重于应力发光纤维的连续化生产,通过搭建连续化生产设备,可大批量应力发光纤维,生产成本较低,适用于实际应用。
对比例1
采用高温固相法烧制闪锌矿结构的含铜元素硫化锌应力发光粉。烧粉参数:称取硫化锌原料400g,添加剂包括:硫酸铜粉末0.656g,氯化钠固体24g,氯化镁固体40g,将添加剂溶解于200ml去离子水中,搅拌溶解;将添加剂溶液与硫化锌原料充分混合;放置烘箱内烘干,烘干条件为温度100℃,时间8h。烘干后,至于1100℃马弗炉中煅烧2h;反应结束后再马弗炉内冷却置室温;使用高温去离子水将粉体进行清洗,去除杂质;清洗后将粉体置于750℃马弗炉中煅烧2.5h,反应结束后再马弗炉内冷却置室温;使用高温去离子水将粉体进行清洗,去除杂质并烘干。得到未包覆的立方相应力发光粉,如图6所示。
取出干燥后的粉体,称取150g,放入300ml 0.5M氢氧化钠溶液中浸泡5h;水洗至中性后干燥;将预处理后的粉体与1500ml缓冲溶液混合,缓冲液pH约为5,搅拌30min;配置浓度为0.1M硫酸铝溶液,取750ml该溶液滴加入发光粉混合体系中,滴加速度为7ml/min;滴加完毕后,加热搅拌1h,加热温度为70℃;反应结束后,向反应体系中滴加氢氧化钠溶液,浓度为0.5M,调节pH为7;静置,洗涤,干燥。得到表面被包覆的立方相应力发光粉,如图6所示。
Claims (10)
1.一种应力发光材料组合物,其特征在于,组合物包括:应力发光粉、纳米粒子、弹性聚合物;其中纳米粒子掺杂含量为应力发光粉的0-30wt%;应力发光粉掺杂含量为弹性聚合物的20-100wt%。
2.根据权利要求1所述组合物,其特征在于,所述纳米粒子为氧化铝或/和二氧化硅纳米粒子,粒径为10~250nm;纳米粒子掺杂含量为应力发光粉的10-20wt%;弹性聚合物为硅胶和/或聚二甲基硅氧烷;所述应力发光材料为表面包覆氧化铝的掺杂铜元素的硫化锌颗粒、掺杂铜元素的硫化锌颗粒中的至少一种。
3.根据权利要求1所述组合物,其特征在于,所述应力发光材料由下列方法制备,包括:
(1)将硫化锌、激活剂、助熔剂混匀,烘干,煅烧,反应结束后取出并置于室温下冷却,然后洗涤,干燥,得到发光粉;
(2)将硫酸铝溶液滴加入发光粉体系中滴加完毕后,60~80℃下反应1-2h,然后调节体系至中性,洗涤,干燥,煅烧,得到应力发光材料。
4.根据权利要求3所述组合物,其特征在于,所述步骤(1)中激活剂为硫酸铜、氯化铜、溴化铜中的一种或多种;助熔剂为氯化钠和氯化镁;所述激活剂中Cu离子浓度为0.1-0.15mol%;氯化钠含量为硫化锌的4-8wt%;氯化镁含量为硫化锌的8-12wt%。
5.根据权利要求3所述组合物,其特征在于,所述步骤(1)中烘干温度为100~120℃,时间5~8h;所述煅烧为1050~1150℃,时间2~4h;干燥温度为60~100℃,时间4~6h。
6.根据权利要求3所述组合物,其特征在于,所述步骤(2)中硫酸铝溶液的浓度为0.1M~0.3M;发光粉体系为发光粉与缓冲液或水组成的混合体系;其中硫酸铝转化为氧化铝,氧化铝含量为硫化锌的5-15wt%;所述步骤(2)中滴速为5~7ml/min;干燥为60~100℃干燥2~4h;煅烧200~400℃下煅烧2~4h。
7.一种应力发光织物,其特征在于,表面涂覆权利要求1所述应力发光材料组合物的弹性织物。
8.一种应力发光纤维,其特征在于,所述表面包覆权利要求1所述应力发光材料组合物的应力发光纤维。
9.一种应力发光纤维的制备方法,包括:
弹性纤维表面包覆权利要求1所述应力发光材料组合物,150~220℃固化,得到应力发光纤维。
或将权利要求1所述应力发光材料组合物进行预固化及脱泡处理,固化温度为60~80℃,固化时间5~10min;注入弹性纤维通过传送设备,依次通过包覆模具进行涂覆,加热装置进行加热固化,所述应力发光纤维制备过程中纤维的传送速度为0.8~5m/min;包覆模具的孔径为1~2mm;加热固化温度为150~220℃。
10.一种权利要求7所述应力发光纤维在智能织物领域中的应用。
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