CN111960845A - 泡沫陶瓷材料、装饰板及制备方法 - Google Patents
泡沫陶瓷材料、装饰板及制备方法 Download PDFInfo
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Abstract
本发明公开了一种泡沫陶瓷材料、装饰板及制备方法,包括:将混合均匀的原料进行研磨,得到混合粉料;对所述混合粉料进行喷水造粒形成粒料;将所述粒料填入模具中进行烧结,烧结完成后退火,获得所述泡沫陶瓷材料。所述原料包括:25‑55份煤矸石、20‑30份低品位铝矾土、5‑10份石灰石、5‑10份长石、1‑10份起泡剂、1‑3份稳泡剂、1‑3份助熔剂。本发明提供的泡沫陶瓷材料具有制备工艺简单、吸水率低、导热系数小以及保温性能好等优点,所采用的原料具有来源广泛、价格低廉、工业固废再利用等优点,且在生产过程中,可以达到对物料的重复再利用,基本实现废料零排放。
Description
技术领域
本发明涉及固体废弃物综合利用和建筑材料技术领域,具体涉及一种泡沫陶瓷材料、装饰板及其制备方法。
背景技术
煤矸石是开采煤炭过程中产生的固体废弃物,我国每年新增煤矸石约3.7~6.6亿吨,产量居世界首位,全国有超过1700个煤矸石山,累积堆存量达到45~50亿吨。煤矸石若不做处理,便进行填埋或露天堆放,不仅占用大量的土地,而且煤矸石中的放射性元素、重金属和多环芳烃化合物等有害物质会对土壤、河流和地下水造成污染,煤矸石自燃释放出的二氧化碳、氮氧化物、二氧化硫等有害气体对大气环境造成污染,危害人体健康。目前我国煤矸石的整体利用率约为65%,其中用于制备建筑材料的煤矸石占总利用量的12%,煤矸石的资源化问题亟待解决。
泡沫陶瓷是一种以陶瓷工艺生产的多孔硅酸盐材料,具有强度高、重量轻、导热系数小而被用在各种保温建筑、设备上。泡沫陶瓷所用原材料十分丰富,除去常用的陶瓷原料之外,尾矿渣、电视机拆解玻璃、冶炼废渣、建筑垃圾及页岩、板岩、煤矸石、粉煤灰等多种硅酸盐固体废弃物均可作为泡沫陶瓷的原料。
但是由于泡沫陶瓷的内部结构较为复杂,在生产过程中,很难形成分布均匀的闭口孔,这对泡沫陶瓷的吸水性能、力学性能、导热性能等有均不利的影响,并且降低了泡沫陶瓷的成品率;并且生产该陶瓷的工艺制程长,操作繁琐,较难控制,不利于大规模的生产,使得产能大大降低。另外由于陶瓷在进行切割工序后,会造成大量的残余边角料,造成了物料的浪费。
发明内容
鉴于上述背景技术存在的问题,本发明提供一种制备泡沫陶瓷材料的方法,包括:
将混合均匀的原料进行研磨,得到混合粉料;
对所述混合粉料进行喷水造粒形成粒料;其中,所述喷水的量为所述混合粉料的5%;
将所述粒料填入模具中进行烧结,烧结完成后退火,获得所述泡沫陶瓷材料;
其中,所述原料包括:25-55份煤矸石、20-30份低品位铝矾土、5-10份石灰石、5-10份长石、1-10份起泡剂、1-3份稳泡剂、1-3份助熔剂。
进一步地,所述制备泡沫陶瓷材料的方法还包括:
将10-20份不合格的所述泡沫陶瓷材料和切割后的边角料破碎后与所述原料混合、研磨,制备所述混合粉料。
进一步地,将所述粒料填入模具中进行烧结,烧结完成后退火,获得所述泡沫陶瓷材料,包括:
将所述粒料填入模具中,然后升温至450℃-500℃,保温时间为20-30min;
保温完成后升温至1000℃-1200℃,发泡50min-70min;
发泡完成后,按照10℃/min-30℃/min的冷却速率冷却至550℃-650℃,然后再自然冷却至室温,获得所述泡沫陶瓷材料。
进一步地,以3℃/min-10℃/min的升温速率升温至450℃-500℃,以5℃/min-15℃/min的升温速率升温至1000℃-1200℃。
进一步地,所述起泡剂选自碳酸钙、二氧化锰和九水硅酸钠的一种或几种,所述稳泡剂选自磷酸三钠和/或无水碳酸钠,所述助熔剂选自硼砂和/或硼酸。
进一步地,所述混合粉料的粒度小于0.088mm。
本发明提供一种由上述任一方法制备的泡沫陶瓷材料。
进一步地,所述泡沫陶瓷材料具有多闭口孔结构,所述闭口孔孔径小于1mm。
所述泡沫陶瓷材料的体积密度为110kg/m3-120kg/m3,抗压强度为1.0MPa-1.5MPa,抗折强度为1.0MPa-1.5MPa,导热系数为0.05W/(m·k)-0.065W/(m·k),体积吸水率0.8%-1.4%。
本发明还提供一种装饰板,其包含以上所述的泡沫陶瓷材料。
本发明提供的泡沫陶瓷材料具有制备工艺简单、吸水率低、导热系数小以及保温性能好等优点,提高微晶泡沫陶瓷成品率和模具内衬陶瓷纤维纸的利用效率,所采用的原料具有来源广泛、价格低廉、工业固废再利用等优点,且在生产过程中,可以达到对物料的重复再利用,基本实现废料零排放。
附图说明
图1为本发明提供的一种制备泡沫陶瓷材料的工艺流程图。
图2是本发明制备的一种泡沫陶瓷材料的放大50倍的扫描电镜图。
图3是图2所示的泡沫陶瓷材料的放大100倍的扫描电镜图。
具体实施方式
下面将对本申请实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本申请一部分实施例,而不是全部的实施例。基于本申请中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本申请保护的范围。
本申请的术语“包括”和“具有”以及它们任何变形,意图在于覆盖不排他的包含。例如包含了一系列步骤或单元的过程、方法、系统、产品或设备没有限定于已列出的步骤或单元,而是可选地还包括没有列出的步骤或单元,或可选地还包括对于这些过程、方法、产品或设备固有的其它步骤或单元。
在本文中提及“实施例”意味着,结合实施例描述的特定特征、结构或特性可以包含在本申请的至少一个实施例中。在说明书中的各个位置出现该短语并不一定均是指相同的实施例,也不是与其它实施例互斥的独立的或备选的实施例。本领域技术人员显式地和隐式地理解的是,本文所描述的实施例可以与其它实施例相结合。
图1所示为本发明提供的一种制备泡沫陶瓷材料的方法,具体地,包括:
将混合均匀的原料进行研磨,得到混合粉料;
对混合粉料进行喷水造粒形成粒料;其中,所述喷水的量为所述混合粉料的5%;
将粒料填入模具中进行烧结,烧结完成后退火,获得泡沫陶瓷材料。
其中,原料包括:25-55份煤矸石、20-30份低品位铝矾土、5-10份石灰石、5-10份长石、1-10份起泡剂、1-3份稳泡剂、1-3份助熔剂。
煤矸石主要含有硅、铝、铁等元素,煤矸石中含有较多高岭石(Al2O3·2SiO2·2H2O)和石英(SiO2)。表1示出了本发明可用的一种煤矸石的化学成分。
表1煤矸石的化学成分/wt%
低品位铝矾土:铝矾土又称矾土或铝土矿,主要成分是氧化铝,系含有杂质的水合氧化铝,是一种土状矿物。表2示出了本发明使用的一种低品位铝矾土的化学成分。
表2铝矾土的化学成分wt%
起泡剂选自碳酸钙、二氧化锰和九水硅酸钠的一种或几种。进一步地,所述泡沫陶瓷材料还可包括稳泡剂和/或助熔剂。所述稳泡剂选自磷酸三钠和/或无水碳酸钠。所述助熔剂选自硼砂和/或硼酸。
进一步地,上述方法还可包括将10-20份不合格的所述泡沫陶瓷材料和切割后的边角料破碎后与所述原料混合、研磨,制备所述混合粉料。
经切割后成品泡沫陶瓷边角料或者检验不合格的泡沫陶瓷产品以原材料的形式加入配料混合工序里,重复循环使用。而这些经过高温烧结的边角料或不合格产品具有很高的活性,在后续的烧制工序中可以发挥积极的作用,经检验效果很好。同时,这种运行方式可以达到物料的重复再利用,基本实现废料零排放。
可选地,混合粉料的粒度小于0.080mm。
可选地,在将原料混合之前,分别对原料进行预处理,具体方式如下:
(1)煤矸石:先将煤矸石经过颚式破碎机破碎至1-2cm,再将煤矸石放入锥形球磨机进行球磨。球料比取10:1,每次球磨煤矸石为1.5kg,加入磨球为15kg,球磨时间为20min。球磨得出煤矸石粉料首先过20目标准筛(孔径为1.0mm),将大颗粒粉料筛除,再将煤矸石细粉料过180目标准筛(孔径为0.088mm);
(2)铝矾土:即低品位铝矾土碎矿,由于含水量较高,需要先将其干燥后进行球磨。球料比取10:1,每次球磨样品为1.5kg,加入磨球为15kg,球磨时间为20min,将赤泥粉料直接过180目标准筛(孔径为0.088mm)。
(3)石灰石和长石:石灰石和长石原料为块状物料,需分别经过颚式破碎机和锤式破碎机两道破碎工序,使粒度达到小于15mm的颗粒级别。再放入锥形球磨机进行球磨。加入磨球15kg、玻化砖为1.5kg,球磨30min。球磨得出玻化砖粉料先过孔径为1.0mm标准筛将大颗粒粉料筛除,再将细粉料过孔径为0.088mm标准筛。
(4)边角料和不合格品:经过切割工序后,会有大量的残余边角料,这些余料的尺寸大小不一,为了达到合适的配料粒度,可将边角料和不合格品送入颚式破碎机进行破碎,再放入锥形球磨机进行球磨。加入磨球15kg、玻化砖为1.5kg,球磨30min。球磨得出玻化砖粉料先过孔径为1.0mm标准筛将大颗粒粉料筛除,再将细粉料过孔径为0.088mm标准筛。
可选地,将所述粒料填入模具中,然后以3℃/min-10℃/min的升温速率升温至450℃-500℃,保温时间为20-30min;保温完成后以5℃/min-15℃/min的升温速率升温至1000℃-1200℃,发泡50min-70min;发泡完成后,按照10℃/min-30℃/min的冷却速率冷却至550℃-650℃,然后再自然冷却至室温,获得所述泡沫陶瓷材料。
图2和图3是不同放大倍数下的泡沫陶瓷材料的扫描电镜图,示出了泡沫陶瓷材料的微观结构图。如图所示,泡沫陶瓷内部疏松多孔,充满了分布均匀的闭口孔和少量开口孔,孔直径均小于1mm。烧成温度过低时,熔融状态物质较少,形成的液相不足以包裹成孔剂产生的气孔,气体有逸出的可能;烧成温度过高时,熔融物粘性降低,此时发泡剂产生的一部分气体会冲破液相物质,导致气体逸出,形成开口孔,导致气孔分布不均匀,开口孔数量增加,且孔壁较薄、直径较大,这对泡沫陶瓷的力学性能、导热性能等均有不利的影响。泡沫陶瓷的吸水性能和导热性能取决于闭口孔的数量。当坯体内的闭口孔在合适的烧成温度,结构发育良好,当温度过高时,坯体内部气体膨胀增大,孔径逐渐增大、孔壁减薄,原有闭口孔会冲破孔壁,胀大贯通,导致吸水率增大。材料内部闭口孔数量越多,导热系数越小,保温效果越好。
泡沫陶瓷材料的强度主要来自尖晶石和堇青石晶相。泡沫陶瓷材料的主晶相为镁铝尖晶石(MgO·Al2O3),此外还含有硅酸二钙(2CaO·SiO2)、堇青石(2MgO·2Al2O3·5SiO2)、石英(SiO2)等。镁铝尖晶石具有热膨胀系数低、熔点高(2135℃)、化学稳定性和抗热震性好等优点,使得泡沫陶瓷的性能稳定。
煤矸石中的高岭石在400~550℃脱水形成偏高岭石,偏高岭石在550~650℃分解形成生成无定形的SiO2和Al2O3,部分SiO2和Al2O3在900~1000℃形成隐晶质铝硅尖晶石;1000~1100℃隐晶质铝硅尖晶石转变为莫来石。
Al2O3·2SiO2·2H2O(高岭石)→Al2O3·2SiO2(偏高岭石)+H2O
Al2O3·2SiO2→Al2O3(无定形)+2SiO2(无定形)
2Al2O3+3SiO2→2Al2O3·3SiO2(铝硅尖晶石)
3(2Al2O3·3SiO2)→2(3Al2O3·2SiO2)(莫来石)+5SiO2
铝矾土中的水铝石在450~650℃脱水形成刚玉假象,这种假象保持着原有水铝石的基本外形,但边界已经模糊不清,温度进一步升高时转变为刚玉;石灰石在650~850℃分解生成CaO;石灰石和铝土矿中的碳酸镁在550~650℃分解形成生成MgO。堇青石和尖晶石在1000~1200℃形成。
Al2O3·H2O(水铝石)-Al2O3(刚玉假象)+H2O
CaCO3→CaO+CO2 MgCO3→MgO+CO2
MgO+Al2O3→MgO·Al2O3(镁铝尖晶石)
2(3Al2O3·2SiO2)+6(MgO·SiO2)+5SiO2→3(2MgO·2Al2O3·5SiO2)(堇青石)
2(MgO·Al2O3)+5SiO2→2MgO·2Al2O3·5SiO2
2CaO+SiO2→2CaO·SiO2
可选地,烧制成型的泡沫陶瓷半成品自然冷却以后,首先脱出模具,然后进入切割成型加工工序。按照既定的规格尺寸标准,对烧制过的半成品进行冷切割加工,切割后的即为成品。
按照《建筑用发泡陶瓷保温板》(JG/T511-2017)标准对所生产泡沫陶瓷的密度、抗压强度、抗折强度、导热系数和体积吸水率进行检测。所生产泡沫陶瓷的基本性能为:体积密度110kg/m3-120kg/m3、抗压强度1.0MPa-1.5MPa、抗折强度1.0MPa-1.5MPa、导热系数0.05W/(m·k)-0.065W/(m·k)、体积吸水率0.8%-1.4%。表3为本发明的泡沫陶瓷材料主要技术项目指标及与其他保温制品的比较。
表3泡沫陶瓷主要技术项目指标及其他保温制品的比较
从表3可知,本发明制备的泡沫陶瓷材料满足《建筑用发泡陶瓷保温板》(JG/T511-2017)标准对应指标要求,可广泛应用于保温阻燃领域。相对于现有的其他保温材料,本发明的泡沫陶瓷材料体积密度大,导热系数高,抗压、耐折强度高,而且使用温度范围广。
实施例1
制备一种泡沫陶瓷材料,其中,煤矸石45份,低品位铝矾土25份,石灰石7份,长石7份,碳酸钙4份,边角料15份,无水碳酸钠2份、硼酸2份。
上述泡沫陶瓷材料的制备过程为:
将各原料分别进行破碎研磨等程序,使其粒度均小于0.088mm。后将按照以上配比进行分别称重后混合,得到混合均匀的混合粉料,再进行研磨,最终混合粉料的粒度小于0.088mm。对混合粉料进行喷水造粒形成粒料,喷水的量为混合粉料质量的5%。后放入装有内衬陶瓷纤维纸的耐火材料碳化硅模具中,经过振实以后送入辊道窑内烧制。先进行预热,从初始温度升温至500℃,预热升温速率为7℃/min,达到500℃时,保温30min。接着从500℃升温至发泡温度,烧结发泡升温速率为9℃/min,发泡温度为1150℃,达到发泡温度时,发泡60min。烧制周期的完成,进入退火降温程序,从发泡温度迅速冷却至600℃为降温阶段,冷却速率为20℃/min,再从600℃自然冷却至室温,退火时间为18h。
经切割后的泡沫陶瓷产品进行质量检验,检验结果合格率≥98%。
实施例2
制备一种装饰板,其中,煤矸石45份,低品位铝矾土25份,石灰石7份,长石7份,二氧化锰4份,边角料15份,无水碳酸钠2份、硼酸2份。
上述装饰板的制备过程为:
将各原料分别进行破碎研磨等程序,使其粒度均小于0.088mm。然后将上述原料按照以上配比进行分别称重后混合,得到混合均匀的混合粉料,再进行研磨,最终混合粉料的粒度小于0.088mm。对混合粉料进行喷水造粒形成粒料,喷水的量为混合粉料质量的5%。后放入装有内衬陶瓷纤维纸的耐火材料碳化硅模具中,经过振实以后送入辊道窑内烧制。先进行预热,从初始温度升温至500℃,预热升温速率为7℃/min,达到500℃时,保温30min。接着从500℃升温至发泡温度,烧结发泡升温速率为9℃/min,发泡温度为1200℃,达到发泡温度时,发泡60min。烧制周期的完成,进入退火降温程序,从发泡温度迅速冷却至600℃为降温阶段,冷却速率为20℃/min,再从600℃自然冷却至室温,退火时间为18h。冷却后,进行切割成形加工工艺,切割后的即为泡沫陶瓷。后将泡沫陶瓷进行打磨、上釉或专用黏结胶等工序,制得装饰板。
以上实施例由原有模具尺寸1.6m×1.6m×0.2m改为1.6m×3.1m×0.32m,使得每m3成品所用模具内衬陶瓷纤维纸由10.11m2降至6.09m2。并且材料成品率由75%提高至85%,以及整个工艺产能提高66%。
本发明提供的泡沫陶瓷材料具有制备工艺简单、吸水率低、导热系数小以及保温性能好等优点,提高微晶泡沫陶瓷成品率和模具内衬陶瓷纤维纸的利用效率,所采用的原料具有来源广泛、价格低廉、工业固废再利用等优点,且在生产过程中,可以达到对物料的重复再利用,基本实现废料零排放。
再次说明,以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书所作的等效结构或等效流程变换,例如各实施例之间技术特征的相互结合,或直接或间接运用在其他相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (10)
1.一种制备泡沫陶瓷材料方法,其特征在于,包括:
将混合均匀的原料进行研磨,得到混合粉料;
对所述混合粉料进行喷水造粒形成粒料;其中,所述喷水的量为所述混合粉料的5%;
将所述粒料填入模具中进行烧结,烧结完成后退火,获得所述泡沫陶瓷材料;
其中,所述原料包括:25-55份煤矸石、20-30份低品位铝矾土、5-10份石灰石、5-10份长石、1-10份起泡剂、1-3份稳泡剂、1-3份助熔剂。
2.根据权利要求1所述的方法,其特征在于,还包括:
将10-20份不合格的所述泡沫陶瓷材料和切割后的边角料破碎后与所述原料混合、研磨,制备所述混合粉料。
3.根据权利要求1所述的方法,其特征在于,将所述粒料填入模具中进行烧结,烧结完成后退火,获得所述泡沫陶瓷材料,包括:
将所述粒料填入模具中,然后升温至450℃-500℃,保温时间为20-30min;
保温完成后升温至1000℃-1200℃,发泡50min-70min;
发泡完成后,按照10℃/min-30℃/min的冷却速率冷却至550℃-650℃,然后再自然冷却至室温,获得所述泡沫陶瓷材料。
4.根据权利要求3所述的方法,其特征在于,以3℃/min-10℃/min的升温速率升温至450℃-500℃,以5℃/min-15℃/min的升温速率升温至1000℃-1200℃。
5.根据权利要求1所述的方法,其特征在于,所述起泡剂选自碳酸钙、二氧化锰和九水硅酸钠的一种或几种,所述稳泡剂选自磷酸三钠和/或无水碳酸钠,所述助熔剂选自硼砂和/或硼酸。
6.根据权利要求1所述的方法,其特征在于,所述混合粉料的粒度小于0.088mm。
7.一种由权利要求1-6中任一所述方法制备的泡沫陶瓷材料。
8.根据权利要求7所述的泡沫陶瓷材料,其特征在于,所述泡沫陶瓷材料具有多闭口孔结构,所述闭口孔孔径小于1mm。
9.根据权利要求7或8所述的泡沫陶瓷材料,其特征在于,所述泡沫陶瓷材料的体积密度为110kg/m3-120kg/m3,抗压强度为1.0MPa-1.5MPa,抗折强度为1.0MPa-1.5MPa,导热系数为0.05W/(m·k)-0.065W/(m·k),体积吸水率0.8%-1.4%。
10.一种装饰板,包含如权利要求7-9中任一所述的泡沫陶瓷材料。
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CN113121257A (zh) * | 2021-05-18 | 2021-07-16 | 烟台大学 | 一种表面致密的超轻全闭孔泡沫陶瓷及其低温烧制方法 |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN112500197A (zh) * | 2020-12-14 | 2021-03-16 | 沈阳建筑大学 | 一体化泡沫陶瓷保温板界面熔烧专用材料及其制备和应用 |
CN112500197B (zh) * | 2020-12-14 | 2022-06-07 | 沈阳建筑大学 | 一体化泡沫陶瓷保温板界面熔烧专用材料及其制备和应用 |
CN114763309A (zh) * | 2021-01-15 | 2022-07-19 | 中国科学院过程工程研究所 | 一种网状孔壁发热元件及其制备方法和应用 |
CN113121257A (zh) * | 2021-05-18 | 2021-07-16 | 烟台大学 | 一种表面致密的超轻全闭孔泡沫陶瓷及其低温烧制方法 |
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