CN110240472B - 一种消防指示用多色系蓄光陶瓷及其制备方法 - Google Patents

一种消防指示用多色系蓄光陶瓷及其制备方法 Download PDF

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CN110240472B
CN110240472B CN201910587345.4A CN201910587345A CN110240472B CN 110240472 B CN110240472 B CN 110240472B CN 201910587345 A CN201910587345 A CN 201910587345A CN 110240472 B CN110240472 B CN 110240472B
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light
storing
ceramic
powder
raw material
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CN110240472A (zh
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张乐
杨顺顺
王蕊
黄今
王湛然
朱晓宇
康健
黄国灿
孙炳恒
周天元
陈浩
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Jiangsu Normal University
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Abstract

本发明公开了一种消防指示用多色系蓄光陶瓷及其制备方法，制备过程是：将玻璃基质原料、长余辉蓄光粉、分散剂和氧化铝粉放入造粒机内，加入掺杂有造孔剂的纯水后直接机械搅拌造粒，搅拌4～8小时后加入增塑剂，继续搅拌1～3小时得到混料，将混料分装进模具中，压片；随后脱模送进窑炉进行干燥并烧制，得到蓄光自发光石英陶瓷；在陶瓷产品表面做花纹打印，并固化得到可用于指示标志的蓄光陶瓷。本发明采用工业废料玻璃作原料，烧结温度低且绿色环保；同时引入弥散分布的气孔和氧化铝做散射源，进一步提高陶瓷的吸光效率和荧光输出相率；作为散射源的氧化铝相又可作为透光介质，提高了陶瓷的透光性，呈现出玉质效果，步骤简单，成本低廉。

Description

一种消防指示用多色系蓄光陶瓷及其制备方法
技术领域
本发明涉及蓄光陶瓷制备技术领域，具体涉及一种消防指示用多色系蓄光陶瓷及其制备方法。
背景技术
蓄光性自发光材料(以下简称为蓄光材料)是通过光源照射在光源消失后的一定时间内仍能自己发光的材料。这种特殊材料可经过日光或灯光等照射后在夜晚或黑暗处发光，因而不存在能源消耗和电池隐患、也无需铺设电路、化学稳定性好且发光时间长等优良理化性能，广泛应用于建筑装饰、交通运输、消防安全、电子通信、地铁隧道、印刷印染、广告牌匾、珠宝首饰等各个领域。
目前在消防指示用蓄光材料的研究上，国内外使用的蓄光型产品的载体材质有薄铝板材(在其上印刷蓄光材料图案)、塑料、油墨、树脂等经过常温或较低温度处理就能定型的材料。其中有“发光涂料+基质”的结构，如CN01231697.0，CN102271912A等；“分层复合”结构，如CN108727734A，CN10385465A，CN101508530A，CN203021440U等；“简单包覆”结构，如CN102765894A，CN10519507A等。然而以上技术虽能产生蓄光自发光效果，但是由于是简单将发光材料涂覆或者混合在基质中，会带来热冲击性差的问题，例如在夏天室外太阳光下曝晒，或者突然下雨时便加速老化，造成“掉渣”现象，特别是一旦发生火灾，带来的高温会很容易造成发光粉体氧化失效或者产品熔融；且存在技术问题加上发光涂层厚度仅在1～2mm的限制条件，此方法显然无法提供足够的发光中心来实现高亮度指示或者照明，其余辉时间也相对较短。
针对以上问题，“蓄光透明陶瓷”概念应运而生。2015年日本Tanabe课题组基于能带工程原理，设计制备了Cr3+-Eu3+共掺的Gd3Al5-xGaxO12长余辉透明陶瓷，其中Eu3+离子承担电子捕获功能而转变为Eu2+，而Ga3+的加入有效地实现了能带裁剪进而改变陷阱深度，实现了UV激发下的730nm深红光发射，其1小时余辉亮度分别是Cr3+:GGG和Cr3+:ZnGa2O4的25倍和6倍；2016年巴西科学家R.S.Silva教授采用激光烧结技术制备了在600-800nm范围内透过率达40％的SrAl2O4:Eu,Dy半透明长余辉陶瓷，但由于激光烧结使Eu3+还原为Eu2+，其余辉时间仅保留45min。但是由于蓄光透明陶瓷余辉陷阱实现方式有限，加上烧制温度相对较高，很容易使蓄光粉发生生热损伤甚至氧化失效，余辉时间短、亮度低。此外，透明陶瓷烧制所需均为高纯原料，价格昂贵且设备条件要求也极为苛刻，因此市场应用潜力极其有限。
与上述材料相比，石英玻璃材料具有强度高、耐候性好、耐水、表面易清洗、使用寿命长等优点。而将蓄光材料的优点与石英玻璃材料的优点集于一身即蓄光自发光玻璃，进一步提升了蓄光材料制品的性能。如发明专利CN1317456A公开了硼硅锌长余辉玻璃的制备方法，但是此方法制备最高需在1350℃～1500℃下加热，随后经淬火或退火过程制备成蓄光玻璃；CN1397509A公布了在常规玻璃制备过程中，在成型过程中(900℃～1300℃)再加入蓄光自发光材料随后成型或者二次加工熔融加入蓄光自发光原料，此过程需要在高温下搅拌均化、澄清；CN586885C公布了先将长余辉发光材料与玻璃粉混合经600℃～1400℃高温固相法或者热压烧结成蓄光玻璃后破碎成玻璃块，然后结合常规玻璃成型工艺，在900℃～1300℃被滚粘并冷却成型；CN1505674A提出同时含有无机骨材或填充材料与树脂混合的材料并加入蓄光自发光粉体制备成蓄光自发光人造石材。
然而，上述结合玻璃制备与蓄光自发光材料的技术虽有可取之处，但还是伴随着一些问题：
(1)资源浪费，大都需要900℃甚至1300℃以上的高温条件，不仅能耗大，还容易使蓄光粉体受到热损伤甚至氧化失效；
(2)工艺条件复杂，制备过程或参考透明陶瓷工艺或参考传统玻璃制备工艺，甚至还会进行二次加工。特别是在玻璃熔融状态下加入蓄光粉的工序，不仅造成大量的热能浪费，还会给工作人员带来重大安全隐患；
(3)设备要求高，有些公开的技术不仅需要高温环境设备，还需要在低压的条件下进行，更有些需要热压烧结和气氛烧结，极大地增加了操作难度和生产成本。
(4)蓄光效率低，由于蓄光陶瓷(折射率为1.45-1.56)与空气(折射率为1.0)间的较大的折射率差，受到外界能量的激发后产生荧光从陶瓷上表面出射时会产生全发射效应，经计算全反射临界角为44°，即只有24.4％的荧光能够从陶瓷上表面出射，实现前置光的提取，其余荧光受限于全反射效应，将在陶瓷内部以波导效应形式传输，直至完全损耗。
发明内容
本发明的目的是提供一种消防指示用多色系蓄光陶瓷及其制备方法，步骤简单，材料易制，成本低廉。
为实现上述目的，本发明采用的技术方案如下：一种消防指示用多色系蓄光陶瓷的制备方法，包括以下步骤：
(1)将玻璃基质原料、长余辉蓄光粉、分散剂和氧化铝粉放入造粒机内，加入掺杂有造孔剂的纯水后直接机械搅拌造粒，搅拌4～8小时后加入增塑剂，继续搅拌1～3小时得到混料，为糊料、砂浆或粘稠物；整个搅拌过程的搅拌转速在100～300rad/min；所述玻璃基质原料选用经回收处理的浮法玻璃废料或工业废旧玻璃；
(2)将步骤(1)得到的混料分装进模具中，利用自动压片机进行压片；模具形状为产品要求所需，压力在5～40MPa，保压时间在5～20s，随后脱模送进窑炉进行干燥并烧制；
(3)窑炉升温制度为：室温～200℃，速率在2～5℃/min，保温10～30min，保证坯体水分完全蒸发；随后继续升温至400～900℃，保温60～120min，保证无色玻璃粉在半熔融状态内完成结晶和晶核长大及气孔排出过程，且不会对长余辉自发光材料造成热损伤；然后随炉冷却至100℃以下取出，得到蓄光自发光石英陶瓷；
(4)在蓄光自发光石英陶瓷产品表面做花纹打印，并在温度300～600℃、时间在20～40min的环境下进行固化获得可用于指示标志的蓄光陶瓷。
优选的，长余辉蓄光粉选用CaAl3O4：Eu，Nb、Sr4Al14O25：Eu，Dy、SrAl2O4：Eu，Dy等铝酸盐体系；Eu，Dy激活的焦硅酸盐蓝色粉，Mg激活的正硅酸盐白色发光粉体等硅酸盐体系；黄绿色的ZnS：Cu系列，蓝色的CaS：Bi系列，红色的CaS：Eu系列等硫化物体系等。
优选的，步骤(1)中，所述玻璃基质原料的粒径为10～400微米；所述长余辉蓄光粉的粒径为10～500微米；所述氧化铝的粒径为10～500纳米；所述分散剂为三聚磷酸钠；所述造孔剂为天然有机细粉；所述增塑剂为甲基纤维素。
优选的，步骤(1)中，所述玻璃基质原料与长余辉蓄光粉的质量比为9～49：1；所述分散剂的添加量占玻璃基质原料与长余辉蓄光粉总质量的0.1～0.6％，所述增塑剂的添加量占玻璃基质原料与长余辉蓄光粉总质量的0.1～0.9％，所述造孔剂的添加量占玻璃基质原料与长余辉蓄光粉总质量的0.1～0.4％，所述氧化铝粉体的添加量占玻璃基质原料与长余辉蓄光粉总质量的0.1～0.4％，所述纯水的添加量占玻璃基质原料与长余辉蓄光粉总质量的20％～50％。
进一步地，步骤(1)中所用的原料还包括用以美化或者符合产品特殊要求所需的与长余辉蓄光粉发光配合的颜料，所述颜料与长余辉蓄光粉的质量比为3.5以下。
本发明还提供由上述制备方法制得的消防指示用多色系蓄光陶瓷，黑暗中可观察到发蓝绿色的光。
与现有技术相比，本发明具有如下有益效果：
1.本发明主要原料之一的无色玻璃粉为经回收处理过的浮法玻璃废料或工业玻璃废料，来源广泛、价格低廉，熔点最低可至400℃，为绿色回收能源。与现有技术相比，采用此原料不仅大大降低了能耗和成本，还有利于废旧建筑玻璃和玻璃残次品的回收利用，减轻环境压力。
2.和现有工艺技术相比，本发明采用一次性机械混合压坯烧制，无需高温条件、无需坩埚辅助成型、无需热压或气氛烧结，生产工序极为简单快捷，避免了取样时对坩埚的破碎和相关高精度烧制设备的采购，极大地降低了能耗和设备采购成本，工作人员的安全系数也大大提高。
3.通过可控引入弥散分布的气孔和氧化铝做散射源，进一步提高陶瓷的吸光效率和荧光输出相率；作为散射源的氧化铝相又可作为透光介质同时提高陶瓷的透光特性，呈现出玉质效果；本发明获得的陶瓷产品，表面光滑、玉质、无缺陷，尺寸达(100～300mm)长/宽×(3～20mm)厚；发光典型波长为520nm绿光、470nm天蓝光等；在20min蓄光的条件下，可实现720min的持续发光：初始1min强度，>4000mcd/m2；60min，>400mcd/m2；720min，>5mcd/m2(室外阳光直射20min，日光灯30min，紫外线5min，室温25℃测试)；
4.使用寿命跟建筑陶瓷同寿命，至少15年以上不老化，水中8年以上，本发明产品所具备的优良性能完全可以胜任消防指示用材料。
附图说明
图1为本发明产品的示意图。
图2为本发明实施例1的产品实物图。
图3为本发明实施例1制备的样品的X射线衍射图谱。
图4为本发明实施例1制备的样品与市售蓄光陶瓷发光及余晖时间对比图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细说明。
下述实施例中，除非另有说明，所述的实验方法通常按照常规条件或制造厂商建议的条件实施；所用的原料、试剂均为市售商品。
以下六个实施例配方如下表所示。
Figure BDA0002114880190000051
实施例1
具体制备方法包括下列步骤：
(1)将粒径400微米的玻璃基质原料、粒径500微米的长余辉蓄光粉(Sr4Al14O25：Eu，Dy)、分散剂三聚磷酸钠和粒径500纳米的氧化铝粉放入造粒机内，加入掺杂有少量粒径0.5微米的造孔剂天然有机细粉的纯水后直接机械搅拌造粒，搅拌8小时后加入增塑剂甲基纤维素，继续搅拌3小时得到混料，为糊料、砂浆或粘稠物；整个搅拌过程的搅拌转速在300rad/min；所述玻璃基质原料选用经回收处理的浮法玻璃废料或工业废旧玻璃；
(2)选用自动压片机将步骤(1)得到的混料分装进模具中进行压片；模具形状为正方形(20cm*20cm)，压力在40MPa，保压时间在20s，随后脱模送进窑炉进行干燥并烧制；
(3)窑炉升温制度为：室温～200℃，速率在5℃/min，保温30min，保证坯体水分完全蒸发；随后继续升温至900℃，升温速率3℃/min，保温120min，保证无色玻璃粉在半熔融状态内完成结晶和晶核长大及气孔排出过程，且不会对长余辉自发光材料造成热损伤；然后随炉冷却至100℃以下取出，得到蓄光自发光石英陶瓷；
(4)将陶瓷产品表面做花纹打印并在温度300℃、时间在20min的环境下进行固化获得可用于指示标志的蓄光陶瓷。
图1为本发明产品的示意图，图中圆形代表长余辉蓄光粉(分散相)，其余为玻璃基质(连续相)，说明陶瓷能通体发光。
图2为本实施例1的产品实物图，黑暗中可观察到发蓝绿色的光。
图3为本实施例1制备的样品的X射线衍射图谱，XRD的测试结果显示，所制备的样品的X射线衍射峰与铝酸锶(PDF(#34-0379))的标准卡片相吻合。此外，XRD图谱在20～40的衍射角范围内，呈现非常明显的馒头峰，证明了非晶态二氧化硅的存在。
图4为本实施例1制备的样品与市售蓄光陶瓷发光及余晖时间对比，测试结果显示，本方法制备的蓄光陶瓷发光初始强度提高了26％。
实施例2
具体制备方法包括下列步骤：
(1)将粒径400微米的玻璃基质原料、粒径500微米的长余辉蓄光粉(Sr4Al14O25：Eu，Dy)、分散剂三聚磷酸钠和粒径500纳米的氧化铝粉放入造粒机内，加入掺杂有少量粒径0.5微米的造孔剂天然有机细粉的纯水后直接机械搅拌造粒，搅拌8小时后加入增塑剂甲基纤维素，继续搅拌3小时得到混料，为糊料、砂浆或粘稠物；整个搅拌过程的搅拌转速在300rad/min；所述玻璃基质原料选用经回收处理的浮法玻璃废料或工业废旧玻璃；
(2)选用自动压片机将步骤(1)得到的混料分装进模具中进行压片；模具形状为正方形片状(20cm*20cm)，压力在40MPa，保压时间在20s，随后脱模送进窑炉进行干燥并烧制；
(3)窑炉升温制度为：室温～200℃，速率在5℃/min，保温30min，保证坯体水分完全蒸发；随后继续升温至900℃，升温速率3℃/min，保温120min，保证无色玻璃粉在半熔融状态内完成结晶和晶核长大及气孔排出过程，且不会对长余辉自发光材料造成热损伤；然后随炉冷却至100℃以下取出，得到蓄光自发光石英陶瓷；
(4)将陶瓷产品表面做花纹打印并在温度300℃、时间在20min的环境下进行固化获得可用于指示标志的蓄光陶瓷。
实施例3
具体制备方法包括下列步骤：
(1)将粒径10微米的玻璃基质原料、粒径10微米的长余辉蓄光粉(SrAl2O4：Eu，Dy)、分散剂三聚磷酸钠和粒径10纳米的氧化铝粉放入造粒机内，加入掺杂有少量粒径10微米的造孔剂天然有机细粉的纯水后直接机械搅拌造粒，搅拌4小时后加入增塑剂甲基纤维素，继续搅拌1小时得到混料，为糊料、砂浆或粘稠物；整个搅拌过程的搅拌转速在100rad/min；所述玻璃基质原料选用经回收处理的浮法玻璃废料或工业废旧玻璃；
(2)选用自动压片机将步骤(1)得到的混料分装进模具中进行压片；模具形状为矩形(20cm*30cm)，压力在5MPa，保压时间在5s，随后脱模送进窑炉进行干燥并烧制；
(3)窑炉升温制度为：室温～200℃，速率在5℃/min，保温10min，保证坯体水分完全蒸发；随后继续升温至400℃，升温速率5℃/min，保温60min，保证无色玻璃粉在半熔融状态内完成结晶和晶核长大及气孔排出过程，且不会对长余辉自发光材料造成热损伤；然后随炉冷却至100℃以下取出，得到蓄光自发光石英陶瓷；
(4)将陶瓷产品表面做花纹打印并在温度600℃、时间在40min的环境下进行固化获得可用于指示标志的蓄光陶瓷。
实施例4
具体制备方法包括下列步骤：
(1)将粒径10微米的玻璃基质原料、粒径10微米的长余辉蓄光粉(SrAl2O4：Eu，Dy)、分散剂三聚磷酸钠和粒径10纳米的氧化铝粉放入造粒机内，加入掺杂有少量粒径10微米的造孔剂天然有机细粉的纯水后直接机械搅拌造粒，搅拌4小时后加入增塑剂甲基纤维素，继续搅拌1小时得到混料，为糊料、砂浆或粘稠物；整个搅拌过程的搅拌转速在100rad/min；所述玻璃基质原料选用经回收处理的浮法玻璃废料或工业废旧玻璃；
(2)选用自动压片机将步骤(1)得到的混料分装进模具中进行压片；模具形状为矩形(20cm*30cm)，压力在5MPa，保压时间在5s，随后脱模送进窑炉进行干燥并烧制；
(3)窑炉升温制度为：室温～200℃，速率在5℃/min，保温10min，保证坯体水分完全蒸发；随后继续升温至400℃，升温速率5℃/min，保温60min，保证无色玻璃粉在半熔融状态内完成结晶和晶核长大及气孔排出过程，且不会对长余辉自发光材料造成热损伤；然后随炉冷却至100℃以下取出，得到蓄光自发光石英陶瓷；
(4)将陶瓷产品表面做花纹打印并在温度600℃、时间在40min的环境下进行固化获得可用于指示标志的蓄光陶瓷。
实施例5
具体制备方法包括下列步骤：
(1)将粒径300微米的玻璃基质原料、粒径200微米的长余辉蓄光粉(SrAl2O4：Eu，Dy)、分散剂三聚磷酸钠和粒径300纳米的氧化铝粉放入造粒机内，加入掺杂有少量粒径0.1微米的造孔剂天然有机细粉的纯水后直接机械搅拌造粒，搅拌6小时后加入增塑剂甲基纤维素，继续搅拌2小时得到混料，为糊料、砂浆或粘稠物；整个搅拌过程的搅拌转速在200rad/min；所述玻璃基质原料选用经回收处理的浮法玻璃废料或工业废旧玻璃；
(2)选用自动压片机将步骤(1)得到的混料分装进模具中进行压片；模具形状为正方形(20cm*20cm)，压力在30MPa，保压时间在15s，随后脱模送进窑炉进行干燥并烧制；
(3)窑炉升温制度为：室温～200℃，速率在3℃/min，保温30min，保证坯体水分完全蒸发；随后继续升温至800℃，升温速率3℃/min，保温120min，保证无色玻璃粉在半熔融状态内完成结晶和晶核长大及气孔排出过程，且不会对长余辉自发光材料造成热损伤；然后随炉冷却至100℃以下取出，得到蓄光自发光石英陶瓷；
(4)将陶瓷产品表面做花纹打印并在温度300℃、时间在30min的环境下进行固化获得可用于指示标志的蓄光陶瓷。
实施例6
具体制备方法包括下列步骤：
(1)将粒径400微米的玻璃基质原料、粒径400微米的长余辉蓄光粉(CaAl3O4：Eu，Nb)、分散剂三聚磷酸钠和粒径300纳米的氧化铝粉放入造粒机内，加入掺杂有少量粒径0.8微米的造孔剂天然有机细粉的纯水后直接机械搅拌造粒，搅拌8小时后加入增塑剂甲基纤维素，继续搅拌2小时得到混料，为糊料、砂浆或粘稠物；整个搅拌过程的搅拌转速在150rad/min；所述玻璃基质原料选用经回收处理的浮法玻璃废料或工业废旧玻璃；
(2)选用自动压片机将步骤(1)得到的混料分装进模具中进行压片；模具形状为正方形(20cm*20cm)，压力在25MPa，保压时间在15s，随后脱模送进窑炉进行干燥并烧制；
(3)窑炉升温制度为：室温～200℃，速率在2℃/min，保温30min，保证坯体水分完全蒸发；随后继续升温至600℃，升温速率2℃/min，保温90min，保证无色玻璃粉在半熔融状态内完成结晶和晶核长大及气孔排出过程，且不会对长余辉自发光材料造成热损伤；然后随炉冷却至100℃以下取出，得到蓄光自发光石英陶瓷；
(4)将陶瓷产品表面做花纹打印并在温度400℃、时间在30min的环境下进行固化获得可用于指示标志的蓄光陶瓷。
以上实施例中，烧制陶瓷用的窑炉可以为辊道窑、梭式窑或者此两种窑炉的改进型，如可进行气氛烧结的辊道窑，可热压烧结或气氛烧结的梭式窑等。
花纹打印用的颜料可以是普通玻璃打印用颜料，也可以是陶瓷打印用颜料。

Claims (3)

1.一种消防指示用多色系蓄光陶瓷的制备方法，其特征在于，包括以下步骤：
（1）将玻璃基质原料、长余辉蓄光粉、分散剂和氧化铝粉放入造粒机内，加入掺杂有造孔剂的纯水后直接机械搅拌造粒，搅拌4~8小时后加入增塑剂，继续搅拌1~3小时得到混料；整个搅拌过程的搅拌转速在100~300 rad/min；所述玻璃基质原料选用经回收处理的浮法玻璃废料或工业废旧玻璃；所述玻璃基质原料的粒径为10~400微米；所述长余辉蓄光粉的粒径为10~500微米；所述氧化铝的粒径为10~500纳米；所述分散剂为三聚磷酸钠；所述造孔剂为天然有机细粉；所述增塑剂为甲基纤维素；所述玻璃基质原料与长余辉蓄光粉的质量比为9~49：1；所述分散剂的添加量占玻璃基质原料与长余辉蓄光粉总质量的0.1~0.6%，所述增塑剂的添加量占玻璃基质原料与长余辉蓄光粉总质量的0.1~0.9%，所述造孔剂的添加量占玻璃基质原料与长余辉蓄光粉总质量的0.1~0.4%，所述氧化铝粉体的添加量占玻璃基质原料与长余辉蓄光粉总质量的0.1~0.4%，所述纯水的添加量占玻璃基质原料与长余辉蓄光粉总质量的20~50%；
（2）将步骤（1）得到的混料分装进模具中，利用自动压片机进行压片；模具形状为产品要求所需，压力在5~40 MPa，保压时间在5~20 s，随后脱模送进窑炉进行干燥并烧制；
（3）窑炉升温制度为：室温~200 ℃，速率在2~5 ℃/min，保温10~30 min；随后继续升温至400~900 ℃，保温60~120 min；然后随炉冷却至100 ℃以下取出，得到蓄光自发光石英陶瓷；
（4）在蓄光自发光石英陶瓷产品表面做花纹打印，并在温度300~600 ℃、时间在20~40min的环境下进行固化获得用于指示标志的蓄光陶瓷。
2.根据权利要求1所述的一种消防指示用多色系蓄光陶瓷的制备方法，其特征在于，步骤（1）中所用的原料还包括用以美化或者符合产品特殊要求所需的与长余辉蓄光粉发光配合的颜料，所述颜料与长余辉蓄光粉的质量比为3.5以下。
3.权利要求1所述的制备方法制得的消防指示用多色系蓄光陶瓷。
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