CN114591059A - 一种用于3d打印的低碳内养护轻质混凝土及其制备方法 - Google Patents
一种用于3d打印的低碳内养护轻质混凝土及其制备方法 Download PDFInfo
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- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明公开了一种用于3D打印的低碳内养护轻质混凝土,由以下质量份组成,磨细煤矸石粉100‑200份、磨细钢渣粉100‑150份、脱硫石膏粉10‑30份、矿渣粉100‑200份、细砂0‑665份、轻骨料270‑600份、氢氧化钠溶液10‑70份、硅酸钠溶液15‑50份、纳米二氧化硅6‑8份、增稠剂3‑4份、减缩剂2‑4份、水260‑350份。制备方法为:将减缩剂溶于拌合水后,加入轻骨料静置吸水之后沥干;将氢氧化钠溶液和硅酸钠溶液溶于剩余的拌合水中,加入煤矸石粉、钢渣粉、脱硫石膏、矿渣混合形成的复合粉体,搅拌形成粘性浆体,加入预湿轻骨料,混合均匀后加入增稠剂和细砂,搅拌制得产物。本发明自重低、收缩小,且大量使用工业废弃物,有利于环保。
Description
技术领域
本发明属于建筑材料技术领域、固体废弃物资源化利用方向,具体涉及一种适用于3D打印的低碳内养护轻质混凝土。
背景技术
近几年,3D打印混凝土技术发展迅速,其特殊的混凝土成型技术要求建筑材料具有优异的触变性能以保证能顺利挤出并迅速站立,因此很多的研究者都在材料配方中加入大量的波特兰水泥或快硬硫铝酸盐水泥以获得更优良的可打印性能和更高的早期强度,但水泥用量越高,对环境和成本带来的负担就越大。
碱激发胶凝材料是一种公认的具有广阔应用前景的新型胶凝材料,主要以粉煤灰、偏高岭土、高炉矿渣、钢渣等工业冶金废渣为原料,与传统水泥生产工艺相比,碱激发胶凝材料的制备可有效降低能耗、同时减少温室气体的排放,是一种环境友好型的绿色低碳胶凝材料。近些年来的研究表明,碱激发胶凝材料具有优异的力学性能,热稳定性等耐久性良好,其速凝、快硬、早强的特性使其具有得以应用在3D打印中的可能性。但已有的研究表明,碱激发材料相对于波特兰水泥具有更大的干燥收缩,而在3D打印混凝土技术中,其层层堆叠的成型方式会放大干燥收缩对打印产品的影响。
发明内容
发明目的:本发明的目的在于提供一种用于3D打印的低碳内养护轻质混凝土,解决了普通3D打印混凝土水泥用量大、干燥收缩大以及自重较高的问题。
技术方案:本发明的用于3D打印的低碳内养护轻质混凝土,所述混凝土包括以下质量份:
磨细煤矸石粉100-200份;
磨细钢渣粉100-150份;
脱硫石膏粉10-30份;
矿渣粉100-200份;
细砂0-665份;
轻骨料270-600份;
氢氧化钠溶液10-70份;
硅酸钠溶液15-50份;
纳米二氧化硅6-8份;
增稠剂3-4份;
减缩剂2-4份;
水260-350份。
进一步地,所述磨细煤矸石粉的制备方法为:将粒状煤矸石进行破碎粉磨后,选取SiO2+Al2O3含量大于80%、比表面积在600m2/kg以上的粉末,先进行600-700℃的微波加热保温2小时,之后使用0.1mol/L的磷酸对粉末进行刻蚀处理1小时,干燥得到磨细煤矸石粉。
进一步地,所述磨细钢渣粉的比表面积为450-650m2/kg;所述脱硫石膏粉的比表面积为400-500m2/kg;矿渣粉的比表面积为400-450m2/kg。
进一步地,所述细砂粒径范围为0.3-0.6mm,饱和面干状态堆积密度为1400-1600kg/m3。
进一步地,所述轻骨料包括黏土、页岩、粉煤灰烧制的陶粒,粒径范围在1-5mm,干燥时堆积密度为500-800kg/m3。
进一步地,所述增稠剂为羟丙基甲基纤维素醚和膨润土的复合增稠剂,具体制备方法为:将羟丙基甲基纤维素醚和去离子水按照质量份数1:(15~30)加入烧杯,水浴加热到40℃,溶解后加入800目钙基膨润土5~8份,在40℃水浴充分搅拌混合,干燥后粉磨得到增稠剂。
进一步地,所述减缩剂的制备方法为:在干燥且通N2的三口烧瓶中加入0.06mol甲基丙烯酸,1.2mol分子量1200的聚乙二醇单甲醚、0.47mol的对苯二酚和0.005mol的对甲基苯磺酸,在140-150℃下反应4小时,冷却至室温后得到酯化反应物;在干燥且通N2的四口烧瓶中加入一定量的蒸馏水,恒温加热至80℃后,同时滴加酯化反应物,0.1mol甲基苯丙烯和0.001mol的过硫酸铵,3小时内滴完,之后95℃保温反应3小时,冷却后滴加10%氢氧化钠溶液,调节pH至6~8左右时得到聚丙烯酸系减缩剂。
本发明还提供一种用于3D打印的低碳内养护轻质混凝土的制备方法,包括以下几个步骤:
S1、将各组分材料按照配方比例称取,将减缩剂加入拌合水中,待减缩剂溶解后,将轻骨料加入拌合水中,静置吸水1小时,之后将预湿轻骨料捞出沥干;
S2、将氢氧化钠溶液和硅酸钠溶液溶于S1中剩余的拌合水中,形成碱激发溶液,待冷至室温后使用;
S3、将磨细煤矸石粉、磨细钢渣粉、脱硫石膏粉、矿渣粉混合形成复合粉体后并搅拌均匀,将S2中制得的碱激发溶液加入复合粉体中,搅拌1-2min,使固体原料从分散状态变成粘性浆体的状态;
S4、将预湿轻骨料加入S3中制得粘性浆体中,搅拌1-2分钟,待轻骨料表面均匀裹上一层浆体后,加入增稠剂和细砂,搅拌3-5分钟后,制得用于3D打印的低碳内养护轻质混凝土。
有益效果:与现有技术相比,本发明具有如下显著优点:
1、煤矸石的化学组成中含有大量的二氧化硅和氧化铝,将其进行微波煅烧之后,煤矸石组成中的高岭石相去除了羟基转变为无序的偏高岭石相,提高其反应活性,用磷酸进一步改性后,提高了煤矸石粉的比表面积,进一步增加了反应活性。
2、脱硫石膏粉的加入一方面在反应前期可以与钢渣粉内部的游离氧化钙和氧化镁反应,生成钙矾石提高产物后期安定性;另一方面为体系中提供了钙源,反应生成硅酸铝钙水合凝胶(C-A-S-H),无定形相趋向于晶体转变,产物更稳定,凝胶体系更致密,弹性模量更高。
3、相较于一般3D打印混凝土配方中高水泥用量,采用煤矸石、钢渣等难以利用的工业废弃物,解决了废弃物排放问题,同时降低了建筑碳排放,更加绿色,对环境更友好。
4、采用级配互补的轻骨料和细砂复配作为集料,在降低了建筑构件整体自重的同时提高了打印产品的表面质量。
5、采用该制备方法可以有效地降低多孔轻骨料在新拌材料中的吸水速率,保持了拌合物浆体的流动性,有效地延长了3D打印轻质混凝土的可打印时间。
6、3D打印混凝土构件暴露面大,干燥收缩也较为严重,采用轻骨料吸收拌合水和减缩剂,在养护后期混凝土孔溶液挥发时,一方面缓慢释放骨料内部水分,提高混凝土内部湿度,另一方面降低混凝土内部孔溶液张力,从而降低建筑构件后期因干燥收缩带来的开裂风险。
具体实施方式
下面对本发明的技术方案作进一步说明。
实施例一
一份用于3D打印的低碳内养护轻质混凝土由以下质量份组成:600m2/kg的磨细煤矸石粉200份、450m2/kg的磨细钢渣粉100份,脱硫石膏粉25份、矿渣粉200份、细砂300份、堆积密度为580kg/m3的黏土陶粒300份、氢氧化钠溶液70份、硅酸钠溶液20份、纳米二氧化硅6份、增稠剂3份、减缩剂3份、水300份。
实施例二、
一份用于3D打印的低碳内养护轻质混凝土由以下质量份组成:650m2/kg的磨细煤矸石粉150份、450m2/kg的磨细钢渣粉150份,脱硫石膏粉30份、矿渣粉200份、细砂400份、堆积密度为680kg/m3的页岩陶粒300份、氢氧化钠溶液45份、硅酸钠溶液45份、纳米二氧化硅6份、增稠剂3份、减缩剂4份、水280份。
实施例三、
一份用于3D打印的低碳内养护轻质混凝土由以下质量份组成:600m2/kg的磨细煤矸石粉100份、550m2/kg的磨细钢渣粉150份,脱硫石膏粉30份、矿渣粉150份、细砂300份、堆积密度为500kg/m3的粉煤灰陶粒500份、氢氧化钠溶液65份、硅酸钠溶液35份、纳米二氧化硅6份、增稠剂3份、减缩剂3份、水350份。
实施例四、
一份用于3D打印的低碳内养护轻质混凝土由以下质量份组成:650m2/kg的磨细煤矸石粉200份、450m2/kg的磨细钢渣粉150份,脱硫石膏粉30份、矿渣粉100份、细砂300份、堆积密度为600kg/m3的黏土陶粒300份、氢氧化钠溶液60份、硅酸钠溶液30份、纳米二氧化硅6份、增稠剂3份、减缩剂3份、水300份。
上述的用于3D打印的低碳内养护轻质混凝土的制备方式如下:
S1、将减缩剂加入拌合水中,待减缩剂溶解后,将轻骨料加入拌合水中,静置吸水1小时,之后将预湿轻骨料捞出沥干;
S2、将氢氧化钠溶液和硅酸钠溶液溶于S1中剩余的拌合水中,形成碱激发溶液,待冷至室温后使用;
S3、将磨细煤矸石粉、磨细钢渣粉、脱硫石膏粉、矿渣粉混合形成复合粉体后并搅拌均匀,将S2中制得的碱激发溶液加入复合粉体中,搅拌1-2min,使固体原料从分散状态变成粘性浆体的状态;
S4、将预湿轻骨料加入S3中制得粘性浆体中,搅拌1-2分钟,待轻骨料表面均匀裹上一层浆体后,加入增稠剂和细砂,搅拌3-5分钟后,制得用于3D打印的低碳内养护轻质混凝土。
对比例一、
普通硅酸盐42.5水泥600份、水180份、纳米二氧化硅6份、中砂900份、羟丙基甲基纤维素类增稠剂3份、聚羧酸类减水剂3份。
对比例二、
600m2/kg的磨细煤矸石粉100份、550m2/kg的磨细钢渣粉150份,脱硫石膏粉30份、矿渣粉150份、细砂600份、堆积密度为500kg/m3的粉煤灰陶粒200份、氢氧化钠溶液65份、硅酸钠溶液35份、纳米二氧化硅6份、增稠剂3份、减缩剂3份、水350份。
对比例三、
600m2/kg的磨细煤矸石粉100份、550m2/kg的磨细钢渣粉150份,脱硫石膏粉30份、矿渣粉150份、细砂100份、堆积密度为500kg/m3的粉煤灰陶粒700份、氢氧化钠溶液65份、硅酸钠溶液35份、纳米二氧化硅6份、增稠剂3份、减缩剂3份、水350份。
实施例一~四及对比例一~三制得的用于3D打印的轻质混凝土的性能检测结果如表1:
表1性能测试结果
对比例一为相同强度等级的普通3D打印混凝土,对比例二相比于实施例三陶粒的添加量小于270份,对比例三相比于实施例三陶粒的添加量大于600份。经过对比发现,相同强度等级的普通3D打印混凝土和本发明3D打印的低碳内养护轻质混凝土相比:本发明密度更低,可打印窗口时间与未掺加吸水材料的对比例相近,其28天的干燥收缩远远低于普通3D打印混凝土。对比例二、三和实施例三相比:陶粒添加量减少,28天的干燥收缩明显增大;陶粒添加过量,混凝土强度降低、成本升高但收缩量并没有明显的改善。
Claims (8)
1.一种用于3D打印的低碳内养护轻质混凝土,其特征在于,所述混凝土包括以下质量份:
磨细煤矸石粉100-200份;
磨细钢渣粉100-150份;
脱硫石膏粉10-30份;
矿渣粉100-200份;
细砂0-665份;
轻骨料270-600份;
氢氧化钠溶液10-70份;
硅酸钠溶液15-50份;
纳米二氧化硅6-8份;
增稠剂3-4份;
减缩剂2-4份;
水260-350份。
2.根据权利要求1所述的用于3D打印的低碳内养护轻质混凝土,其特征在于,所述磨细煤矸石粉的制备方法为:将粒状煤矸石进行破碎粉磨后,选取SiO2+Al2O3含量大于80%、比表面积在600m2/kg以上的粉末,先进行600-700℃的微波加热保温2小时,之后使用0.1mol/L的磷酸对粉末进行刻蚀处理1小时,干燥得到磨细煤矸石粉。
3.根据利要求1所述的用于3D打印的低碳内养护轻质混凝土,其特征在于,所述磨细钢渣粉的比表面积为450-650m2/kg;所述脱硫石膏粉的比表面积为400-500m2/kg;矿渣粉的比表面积为400-450m2/kg。
4.根据利要求1所述的用于3D打印的低碳内养护轻质混凝土,其特征在于,所述细砂粒径范围为0.3-0.6mm,饱和面干状态堆积密度为1400-1600kg/m3。
5.根据利要求1所述的用于3D打印的低碳内养护轻质混凝土,其特征在于,所述轻骨料包括黏土、页岩、粉煤灰烧制的陶粒,粒径范围在1-5mm,干燥时堆积密度为500-800kg/m3。
6.根据权利要求1所述的用于3D打印的低碳内养护轻质混凝土,其特征在于,所述增稠剂为羟丙基甲基纤维素醚和膨润土的复合增稠剂,具体制备方法为:将羟丙基甲基纤维素醚和去离子水按照质量份数1:15~30加入烧杯,水浴加热到40℃,溶解后加入800目钙基膨润土5~8份,在40℃水浴充分搅拌混合,干燥后粉磨得到增稠剂。
7.根据权利要求1所述的用于3D打印的低碳内养护轻质混凝土,其特征在于,所述减缩剂的制备方法为:在干燥且通N2的三口烧瓶中加入0.06mol甲基丙烯酸,1.2mol分子量1200的聚乙二醇单甲醚、0.47mol的对苯二酚和0.005mol的对甲基苯磺酸,在140-150℃下反应4小时,冷却至室温后得到酯化反应物;在干燥且通N2的四口烧瓶中加入一定量的蒸馏水,恒温加热至80℃后,同时滴加酯化反应物,0.1mol甲基苯丙烯和0.001mol的过硫酸铵,3小时内滴完,之后95℃保温反应3小时,冷却后滴加10%氢氧化钠溶液,调节pH至6~8左右时得到聚丙烯酸系减缩剂。
8.一种权利要求1所述的用于3D打印的低碳内养护轻质混凝土的制备方法,其特征在于,包括以下几个步骤:
S1、将各组分材料按照配方比例称取,将减缩剂加入拌合水中,待减缩剂溶解后,将轻骨料加入拌合水中,静置吸水1小时,之后将预湿轻骨料捞出沥干;
S2、将氢氧化钠溶液和硅酸钠溶液溶于S1中剩余的拌合水中,形成碱激发溶液,待冷至室温后使用;
S3、将磨细煤矸石粉、磨细钢渣粉、脱硫石膏粉、矿渣粉混合形成复合粉体后并搅拌均匀,将S2中制得的碱激发溶液加入复合粉体中,搅拌1-2min,使固体原料从分散状态变成粘性浆体的状态;
S4、将预湿轻骨料加入S3中制得粘性浆体中,搅拌1-2分钟,待轻骨料表面均匀裹上一层浆体后,加入增稠剂和细砂,搅拌3-5分钟后,制得用于3D打印的低碳内养护轻质混凝土。
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