CN109208324A - 一种内膨胀纳米孔绝热材料的制备方法 - Google Patents
一种内膨胀纳米孔绝热材料的制备方法 Download PDFInfo
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Abstract
本发明属于绝热材料制备技术领域,具体涉及一种内膨胀纳米孔绝热材料的制备方法。本发明用硅藻土和膨润土制备得到混合粘土,将混合粘土、纳米二氧化硅气凝胶混合制得纳米二氧化硅气凝胶浆液,将混合浆液、纳米二氧化硅气凝胶浆液加热得到熔融料液,将硼化锆粉末、浓缩液等混合高速分散得到纳米增强乳液,先倒入纳米增强乳液,填充耐高温无机填料,压滤烘干得到内膨胀纳米孔绝热材料,本发明中可膨胀石墨对绝热材料内层起到降温作用,同时也起到增强保护作用,反应形成的二氧化锆‑二氧化硅薄膜,进一步提高绝热材料在高温时的耐压强度,应用前景广阔。
Description
技术领域
本发明属于绝热材料制备技术领域,具体涉及一种内膨胀纳米孔绝热材料的制备方法。
背景技术
随着社会经济的发展和人们节能意识的提高,能源节约已成为工业发展中的重点关注对象。绝热材料是指能阻滞热流传递的材料,又称热绝缘材料。它们广泛应用于建筑围护或者热工设备、阻抗热流传递的材料或者材料复合体,既包括保温材料,也包括保冷材料。绝热材料一方面满足了建筑空间或热工设备的热环境,另一方面也节约了能源。因此,有些国家将绝热材料看作是继煤炭、石油、天然气、核能之后的“第五大能”。
常用的绝热材料如石棉、玻璃棉、岩棉、硅酸铝纤维、微孔硅酸钙、泡沫玻璃、膨胀珍珠岩等材料,在常温下有较低的导热系数,但随着温度的升高,它的热导率也会快速递升,特别在高温区热导率递升更快。随着科学技术的进步,纳米孔绝热材料正逐步被应用。纳米孔绝热材料具有纤细的纳米网络结构,能够有效地限制局域激发的传播,其固态热导率可比相应的玻璃态材料低2~3个数量级;又由于其孔洞尺寸通常在几到几十纳米,比常压下气体分子的平均自由程小,微孔洞内的气体分子对热传导的的贡献受到抑制,是一种理想的绝热材料。
纳米孔绝热材料虽然具有优异的绝热性能,但是目前市售的纳米孔绝热材料存在以下缺陷:(1)强度低、韧性差,制品抗压强度一般仅为1.0~1.3MPa;(2)高温的收缩率比较大,在高温条件下应用时,给设备的正常运行带来了极大的风险,安全系数低,严重制约了此种材料在高温设备上的应用;(3)吸水性较大,如果有水进入则会直接导致纳米孔结构塌陷;(4)制备工艺复杂、能耗大、产量小、成本高,价格是普通绝热材料的几十倍,甚至上百倍,制约了纳米孔绝热材料的广泛应用。
因此,提供一种容重小、导热系数低、热稳定性强的绝热材料及其制备方法具有重要意义。
发明内容
本发明主要解决的技术问题,针对目前纳米孔绝热材料强度低、韧性差,绝热材料高温收缩率比较大,在高温条件下应用时,给设备的正常运行带来了极大的风险,安全系数低,严重制约了此种材料在高温设备上的应用的缺陷,提供了一种内膨胀纳米孔绝热材料的制备方法。
为了解决上述技术问题,本发明所采用的技术方案是:
一种内膨胀纳米孔绝热材料的制备方法,其特征在于具体制备步骤为:
(1)按重量份数计,向400~500份水中加入70~80份高岭土、20~30份氧化铝、10~15份钛白粉、20~22份磷酸铝,搅拌分散制成悬浮浆液,向悬浮浆液中加入磷酸溶液调节悬浮浆液的pH值,加热升温,保温,得到混合浆液;
(2)将膨润土研磨后过筛,再经高温煅烧,得到轻烧膨润土,将20~30份硅藻土、10~15份轻烧膨润土混合过筛,得到混合粘土,将35~50份纳米二氧化硅气凝胶、30~40份上述混合粘土、200~300份水混合得到纳米二氧化硅气凝胶浆液;
(3)将混合浆液、纳米二氧化硅气凝胶浆液混合,加热,得到熔融料液,经纺丝得到改性硅酸铝纤维,将改性硅酸铝纤维短切成定长短切纤维,通过开松梳理后铺成网,再针刺制得硅酸铝纤维毡;
(4)取150~200mL甲基硅油加入带有温度计和回流装置的三口烧瓶中,在氮气保护下将三口烧瓶移入沙浴锅中,保温反应后,升温继续保温反应,反应结束后自然冷却至室温,得到产物;
(5)向上述产物中加入200~300mL二甲苯,搅拌混合10~15min后过滤,得到滤液,将滤液转入旋转蒸发仪中,旋蒸浓缩,得到浓缩液,取30~40g硼化锆加入到粉碎机中粉碎30~40min,得到硼化锆粉末,将硼化锆粉末、浓缩液、100~200mL去离子水混合,高速分散后,得到纳米增强乳液;
(6)按重量份数计,将40~50份白刚玉、30~40份黑曜岩、20~25份可膨胀石墨、10~15份石墨烯加入到粉碎机中粉碎,得到耐高温无机填料,将硅酸铝纤维毡放入板框压滤机中,先倒入纳米增强乳液,填满硅酸铝纤维毡孔隙后,再填充20~25份耐高温无机填料,压滤,随后放入真空干燥箱中烘干,得到内膨胀纳米孔绝热材料。
步骤(1)所述的磷酸溶液的质量分数为20%,调节悬浮浆液的pH值为5~6,加热升温后温度为50~60℃,保温时间为10~15h。
步骤(2)所述的所过筛规格为400目,高温煅烧温度为600~800℃,煅烧时间为2~4h。
步骤(3)所述的混合浆液、纳米二氧化硅气凝胶浆液混合体积比为4:1,加热后温度为700~800℃,定长短切纤维长度为50~100mm。
步骤(4)所述的控制沙浴温度为420~430℃,保温反应时间为1~2h,升温后温度为460~480℃,继续保温反应时间为40~50min。
步骤(5)所述的旋转蒸发温度为80~90℃,旋蒸浓缩时间为40~50min,高速分散转速为2500~3000r/min,高速分散时间为15~20min。
步骤(6)所述的粉碎后颗粒直径为1~3mm,纳米增强乳液在板框压滤机中填充深度为4~5mm,压滤时压力为0.7~0.8MPa,真空干燥箱设定温度为70~80℃,烘干时间为2~3h。
本发明的有益效果是:
(1)本发明以高岭土粉体、氧化铝、钛白粉、磷酸铝为原料制成悬浮浆液,加入磷酸调节pH后得到混合浆液,用硅藻土和轻烧膨润土制备得到混合粘土,将混合粘土、纳米二氧化硅气凝胶混合制得纳米二氧化硅气凝胶浆液,将混合浆液、纳米二氧化硅气凝胶浆液混合加热熔融,得到熔融料液,经过纺丝得到改性硅酸铝纤维,将甲基硅油置于高温条件下裂解,得到裂解产物,将裂解产物与二甲苯混溶,经过滤、旋转蒸发得到浓缩液,将硼化锆粉末、浓缩液、水混合高速分散得到纳米增强乳液,将白刚玉、黑曜岩、可膨胀石墨、石墨烯粉碎后得到耐高温无机填料,将硅酸铝纤维毡放入板框压滤机中,先倒入纳米增强乳液,填满硅酸铝纤维毡孔隙后,填充耐高温无机填料,压滤后烘干得到内膨胀纳米孔绝热材料,本发明中添加的膨润土经过高温煅烧后,其内部会形成微气孔并抑制颗粒之间的过烧,其中可膨胀性石墨会侵入微气孔中,在经受高温作用后,由于可膨胀石墨导热系数大,在绝热材料的传热过程中,绝热材料的表面快速升温,膨胀石墨会微膨胀由卷曲状态变为舒张状态,提高绝热材料的外表面散热面积,对绝热材料内层起到降温作用,绝热材料表面的改性硅酸铝纤维熔点高,韧性强,对绝热材料也起到增强保护作用,白刚玉、黑曜岩、可膨胀石墨组合制备的耐高温无机填料在高温时能够膨胀,能够缓冲绝热材料高温收缩变形,并形成一层隔热层,提高绝热材料的保温性能;
(2)本发明所制备的绝热材料以硅酸铝纤维毡作为上下层,中间填充纳米增强乳液和耐高温无机填料,利用甲基硅油所制备的浓缩液为聚碳硅烷,以聚碳硅烷和硼化锆作为纳米增强乳液的增强结合成分,提高填料与硅酸铝纤维毡的界面结合力,使内部耐高温填料可通过膨胀来补充绝热材料的高温收缩,减少绝热材料的高温变形,绝热材料中聚碳硅烷在高温下会裂解为碳化硅晶须,碳化硅晶须填充于绝热材料中可减小气孔孔径,提高绝热材料的高温时的抗压强度,耐高温填料和石墨烯通过聚碳硅烷紧密结合,再经高温烧成后通过碳化硅结合,由于碳化硅具有极高的结合强度,并且碳化硅在高温氧化后可在绝热材料内表面形成一层致密的、牢固的二氧化硅薄膜,另外,碳化硅还可与硼化锆在高温下反应形成二氧化锆-二氧化硅薄膜,从而进一步提高绝热材料在高温时的耐压强度,加入的石墨烯和可膨胀石墨可使绝热材料中无机填料在高温膨胀后内部接触更加紧密润滑,减小高温过程中因膨胀产生的向外应力,从而提高绝热材料在高温环境下的抗压强度和韧性,应用前景广阔。
具体实施方式
按重量份数计,向400~500份水中加入70~80份高岭土、20~30份氧化铝、10~15份钛白粉、20~22份磷酸铝,搅拌分散制成悬浮浆液,向悬浮浆液中加入质量分数为20%的磷酸溶液调节悬浮浆液的pH值至5~6,加热升温至50~60℃,保温10~15h,得到混合浆液;将膨润土研磨后过400目筛,再经600~800℃的高温煅烧2~4h,得到轻烧膨润土,将20~30份硅藻土、10~15份轻烧膨润土混合过400目筛,得到混合粘土,将35~50份纳米二氧化硅气凝胶、30~40份上述混合粘土、200~300份水混合得到纳米二氧化硅气凝胶浆液;将混合浆液、纳米二氧化硅气凝胶浆液按体积比为4:1混合,加热至700~800℃,得到熔融料液,经纺丝得到改性硅酸铝纤维,将改性硅酸铝纤维短切成长度为50~100mm的定长短切纤维,通过开松梳理后铺成网,再针刺制得硅酸铝纤维毡;取150~200mL甲基硅油加入带有温度计和回流装置的三口烧瓶中,在氮气保护下将三口烧瓶移入沙浴锅中,控制沙浴温度为420~430℃,保温反应1~2h后,升温至460~480℃,继续保温反应40~50min,反应结束后自然冷却至室温,得到产物;向上述产物中加入200~300mL二甲苯,搅拌混合10~15min后过滤,得到滤液,将滤液转入旋转蒸发仪中,在80~90℃下旋蒸浓缩40~50min,得到浓缩液,取30~40g硼化锆加入到粉碎机中粉碎30~40min,得到硼化锆粉末,将硼化锆粉末、浓缩液、100~200mL去离子水混合,以2500~3000r/min的转速高速分散15~20min后,得到纳米增强乳液;按重量份数计,将40~50份白刚玉、30~40份黑曜岩、20~25份可膨胀石墨、10~15份石墨烯加入到粉碎机中粉碎至颗粒直径为1~3mm,得到耐高温无机填料,将硅酸铝纤维毡放入板框压滤机中,先倒入深度为4~5mm的纳米增强乳液,填满硅酸铝纤维毡孔隙后,再填充20~25份耐高温无机填料,以0.7~0.8MPa的压力压滤30~35min,随后放入设定温度为70~80℃的真空干燥箱中烘干2~3h,得到内膨胀纳米孔绝热材料。
实例1
按重量份数计,向400份水中加入70份高岭土、20份氧化铝、10份钛白粉、20份磷酸铝,搅拌分散制成悬浮浆液,向悬浮浆液中加入质量分数为20%的磷酸溶液调节悬浮浆液的pH值至5,加热升温至50℃,保温10h,得到混合浆液;将膨润土研磨后过400目筛,再经600℃的高温煅烧2h,得到轻烧膨润土,将20份硅藻土、10份轻烧膨润土混合过400目筛,得到混合粘土,将35份纳米二氧化硅气凝胶、30份上述混合粘土、200份水混合得到纳米二氧化硅气凝胶浆液;将混合浆液、纳米二氧化硅气凝胶浆液按体积比为4:1混合,加热至700℃,得到熔融料液,经纺丝得到改性硅酸铝纤维,将改性硅酸铝纤维短切成长度为50mm的定长短切纤维,通过开松梳理后铺成网,再针刺制得硅酸铝纤维毡;取150mL甲基硅油加入带有温度计和回流装置的三口烧瓶中,在氮气保护下将三口烧瓶移入沙浴锅中,控制沙浴温度为420℃,保温反应1h后,升温至460℃,继续保温反应40min,反应结束后自然冷却至室温,得到产物;向上述产物中加入200mL二甲苯,搅拌混合10min后过滤,得到滤液,将滤液转入旋转蒸发仪中,在80℃下旋蒸浓缩40min,得到浓缩液,取30g硼化锆加入到粉碎机中粉碎30min,得到硼化锆粉末,将硼化锆粉末、浓缩液、100mL去离子水混合,以2500r/min的转速高速分散15min后,得到纳米增强乳液;按重量份数计,将40份白刚玉、30份黑曜岩、20份可膨胀石墨、10份石墨烯加入到粉碎机中粉碎至颗粒直径为1mm,得到耐高温无机填料,将硅酸铝纤维毡放入板框压滤机中,先倒入深度为4mm的纳米增强乳液,填满硅酸铝纤维毡孔隙后,再填充20份耐高温无机填料,以0.7MPa的压力压滤30min,随后放入设定温度为70℃的真空干燥箱中烘干2h,得到内膨胀纳米孔绝热材料。
实例2
按重量份数计,向450份水中加入75份高岭土、25份氧化铝、13份钛白粉、21份磷酸铝,搅拌分散制成悬浮浆液,向悬浮浆液中加入质量分数为20%的磷酸溶液调节悬浮浆液的pH值至5,加热升温至55℃,保温13h,得到混合浆液;将膨润土研磨后过400目筛,再经700℃的高温煅烧3h,得到轻烧膨润土,将25份硅藻土、13份轻烧膨润土混合过400目筛,得到混合粘土,将47份纳米二氧化硅气凝胶、35份上述混合粘土、250份水混合得到纳米二氧化硅气凝胶浆液;将混合浆液、纳米二氧化硅气凝胶浆液按体积比为4:1混合,加热至750℃,得到熔融料液,经纺丝得到改性硅酸铝纤维,将改性硅酸铝纤维短切成长度为75mm的定长短切纤维,通过开松梳理后铺成网,再针刺制得硅酸铝纤维毡;取170mL甲基硅油加入带有温度计和回流装置的三口烧瓶中,在氮气保护下将三口烧瓶移入沙浴锅中,控制沙浴温度为425℃,保温反应1h后,升温至470℃,继续保温反应45min,反应结束后自然冷却至室温,得到产物;向上述产物中加入25mL二甲苯,搅拌混合13min后过滤,得到滤液,将滤液转入旋转蒸发仪中,在85℃下旋蒸浓缩45min,得到浓缩液,取35g硼化锆加入到粉碎机中粉碎35min,得到硼化锆粉末,将硼化锆粉末、浓缩液、150mL去离子水混合,以2750r/min的转速高速分散17min后,得到纳米增强乳液;按重量份数计,将45份白刚玉、35份黑曜岩、23份可膨胀石墨、13份石墨烯加入到粉碎机中粉碎至颗粒直径为2mm,得到耐高温无机填料,将硅酸铝纤维毡放入板框压滤机中,先倒入深度为4mm的纳米增强乳液,填满硅酸铝纤维毡孔隙后,再填充23份耐高温无机填料,以0.7MPa的压力压滤33min,随后放入设定温度为75℃的真空干燥箱中烘干2h,得到内膨胀纳米孔绝热材料。
实例3
按重量份数计,向500份水中加入80份高岭土、30份氧化铝、15份钛白粉、22份磷酸铝,搅拌分散制成悬浮浆液,向悬浮浆液中加入质量分数为20%的磷酸溶液调节悬浮浆液的pH值至6,加热升温至60℃,保温15h,得到混合浆液;将膨润土研磨后过400目筛,再经800℃的高温煅烧4h,得到轻烧膨润土,将30份硅藻土、15份轻烧膨润土混合过400目筛,得到混合粘土,将50份纳米二氧化硅气凝胶、40份上述混合粘土、300份水混合得到纳米二氧化硅气凝胶浆液;将混合浆液、纳米二氧化硅气凝胶浆液按体积比为4:1混合,加热至800℃,得到熔融料液,经纺丝得到改性硅酸铝纤维,将改性硅酸铝纤维短切成长度为100mm的定长短切纤维,通过开松梳理后铺成网,再针刺制得硅酸铝纤维毡;取200mL甲基硅油加入带有温度计和回流装置的三口烧瓶中,在氮气保护下将三口烧瓶移入沙浴锅中,控制沙浴温度为430℃,保温反应2h后,升温至480℃,继续保温反应50min,反应结束后自然冷却至室温,得到产物;向上述产物中加入300mL二甲苯,搅拌混合15min后过滤,得到滤液,将滤液转入旋转蒸发仪中,在90℃下旋蒸浓缩50min,得到浓缩液,取40g硼化锆加入到粉碎机中粉碎40min,得到硼化锆粉末,将硼化锆粉末、浓缩液、200mL去离子水混合,以3000r/min的转速高速分散20min后,得到纳米增强乳液;按重量份数计,将50份白刚玉、40份黑曜岩、25份可膨胀石墨、15份石墨烯加入到粉碎机中粉碎至颗粒直径为3mm,得到耐高温无机填料,将硅酸铝纤维毡放入板框压滤机中,先倒入深度为5mm的纳米增强乳液,填满硅酸铝纤维毡孔隙后,再填充25份耐高温无机填料,以0.8MPa的压力压滤35min,随后放入设定温度为80℃的真空干燥箱中烘干3h,得到内膨胀纳米孔绝热材料。
对比例以北京市某公司生产的绝热材料作为对比例对本发明制得的内膨胀纳米孔绝热材料和对比例中的绝热材料进行检测,检测结果如表1所示:
参照标准JC/T990-2006进行测试。
表1性能测定结果
根据表1中数据可知,本发明制得的内膨胀纳米孔绝热材料,强度高、导热率低、容重小、耐高温性好,具有“硬而不脆、轻而不碎”的特性,此外本发明生产工艺成本低,经济效益好,具有十分广泛的工业化应用前景和市场价值。
Claims (7)
1.一种内膨胀纳米孔绝热材料的制备方法,其特征在于具体制备步骤为:
(1)按重量份数计,向400~500份水中加入70~80份高岭土、20~30份氧化铝、10~15份钛白粉、20~22份磷酸铝,搅拌分散制成悬浮浆液,向悬浮浆液中加入磷酸溶液调节悬浮浆液的pH值,加热升温,保温,得到混合浆液;
(2)将膨润土研磨后过筛,再经高温煅烧,得到轻烧膨润土,将20~30份硅藻土、10~15份轻烧膨润土混合过筛,得到混合粘土,将35~50份纳米二氧化硅气凝胶、30~40份上述混合粘土、200~300份水混合得到纳米二氧化硅气凝胶浆液;
(3)将混合浆液、纳米二氧化硅气凝胶浆液混合,加热,得到熔融料液,经纺丝得到改性硅酸铝纤维,将改性硅酸铝纤维短切成定长短切纤维,通过开松梳理后铺成网,再针刺制得硅酸铝纤维毡;
(4)取150~200mL甲基硅油加入带有温度计和回流装置的三口烧瓶中,在氮气保护下将三口烧瓶移入沙浴锅中,保温反应后,升温继续保温反应,反应结束后自然冷却至室温,得到产物;
(5)向上述产物中加入200~300mL二甲苯,搅拌混合10~15min后过滤,得到滤液,将滤液转入旋转蒸发仪中,旋蒸浓缩,得到浓缩液,取30~40g硼化锆加入到粉碎机中粉碎30~40min,得到硼化锆粉末,将硼化锆粉末、浓缩液、100~200mL去离子水混合,高速分散后,得到纳米增强乳液;
(6)按重量份数计,将40~50份白刚玉、30~40份黑曜岩、20~25份可膨胀石墨、10~15份石墨烯加入到粉碎机中粉碎,得到耐高温无机填料,将硅酸铝纤维毡放入板框压滤机中,先倒入纳米增强乳液,填满硅酸铝纤维毡孔隙后,再填充20~25份耐高温无机填料,压滤,随后放入真空干燥箱中烘干,得到内膨胀纳米孔绝热材料。
2.根据权利要求1所述的一种内膨胀纳米孔绝热材料的制备方法,其特征在于:步骤(1)所述的磷酸溶液的质量分数为20%,调节悬浮浆液的pH值为5~6,加热升温后温度为50~60℃,保温时间为10~15h。
3.根据权利要求1所述的一种内膨胀纳米孔绝热材料的制备方法,其特征在于:步骤(2)所述的所过筛规格为400目,高温煅烧温度为600~800℃,煅烧时间为2~4h。
4.根据权利要求1所述的一种内膨胀纳米孔绝热材料的制备方法,其特征在于:步骤(3)所述的混合浆液、纳米二氧化硅气凝胶浆液混合体积比为4:1,加热后温度为700~800℃,定长短切纤维长度为50~100mm。
5.根据权利要求1所述的一种内膨胀纳米孔绝热材料的制备方法,其特征在于:步骤(4)所述的控制沙浴温度为420~430℃,保温反应时间为1~2h,升温后温度为460~480℃,继续保温反应时间为40~50min。
6.根据权利要求1所述的一种内膨胀纳米孔绝热材料的制备方法,其特征在于:步骤(5)所述的旋转蒸发温度为80~90℃,旋蒸浓缩时间为40~50min,高速分散转速为2500~3000r/min,高速分散时间为15~20min。
7.根据权利要求1所述的一种内膨胀纳米孔绝热材料的制备方法,其特征在于:步骤(6)所述的粉碎后颗粒直径为1~3mm,纳米增强乳液在板框压滤机中填充深度为4~5mm,压滤时压力为0.7~0.8MPa,真空干燥箱设定温度为70~80℃,烘干时间为2~3h。
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