CN115043604B - 一种低本底水泥的制备方法及低本底水泥 - Google Patents
一种低本底水泥的制备方法及低本底水泥 Download PDFInfo
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Abstract
本发明公开了一种低本底水泥及其制备方法。低本底水泥由92.0%~98.0%低本底熟料和2.0%~8.0%石膏共同粉磨制成。其中,低本底熟料通过1.0~5.0%低本底水泥晶种、1.0~5.0%C4AF晶须与90%~98%高镁生料均匀混合后于1400~1500℃条件下煅烧制得。本发明明确了不同原材料的放射性核素比活度,通过对低本底的原材料的控制和限定,保障低本底水泥的稳定制备。其中,低本底水泥晶种为一种高镁中热熟料,其Ra‑226放射性核素比活度控制在50Bq/kg以内,熟料中MgO含量控制在4.0%~5.0%,50%≤C3S≤55.0%;C4AF晶须中游离氧化钙0.3%≤≤2.0%,尺寸控制在直径0.1~0.3mm,长度5.0mm~30.0mm,其Ra‑226放射性核素比活度控制在50Bq/kg以内;依据本发明可实现低本底水泥的工业化稳定制备,获得Ra‑226放射性核素比活度低于50Bq/kg的低本底水泥,为低本底实验室建设提供技术支撑。
Description
技术领域
本发明涉及特种水泥技术领域,具体涉及一种低本底水泥及其制备方法。
背景技术
低本底地下实验室是开展诸如以暗物质为代表的物理学重大基础前沿科学研究的重要场所,对于屏蔽宇宙射线干扰、提高试验研究精度和准确度具有重要作用。伴随科学技术进步,对暗物质的研究得以深入推进,按照原有技术标准要求建成的低本底实验室已无法完全满足实验探索新要求,采取低本底的建筑材料来降低实验环境本底辐射是构筑“超净低本底地下实验室”的重要路径。
通常在核电工程、军事工事、物理实验室建等领域建筑材料往往关注材料的抗辐射性能,针对降低建筑自身本底辐射的研究较为欠缺,少数研究提出低本底混凝土配合比的设计,但仅简单采取多种低本底材料复配方式,没有低本底水泥稳定制备的方法研究。中国发明专利CN103803901公开了一种重晶石抗辐射泵送混凝土,该发明通过添加价格昂贵的重晶石来实现混凝土的抗辐射;中国发明专利CN103755204公开了混凝土添加剂领域中特别是一种抗裂防辐射的混凝土添加剂,该发明也通过添加重晶石及其他添加剂来实现防辐射性能;中国发明专利CN104817304b公开了一种利用含硼矿山尾矿制备抗辐射混凝土方法,通过添加含硼矿山尾矿来实现混凝土的抗辐射。但是,上述发明均不能有效降低本底值,且添加的其他材料会造成混凝土辐射本底值的增加,为此只能选用低辐射低的石英石、石英砂以及聚羧酸无机复合材料减水剂作为原材料配置低本底值混凝土。中国发明专利CN107721322B公开了一种低本底值混凝土中提到使用一种PN42.5核电工程用水泥,并对其放射性核素比活度上限值做出要求,其中Ra-226核素含量上限为19.4,但未给出相应水泥的稳定制备方法,因此,目前低本底水泥的生产、检测和使用尚无规范的技术标准可以遵循,且没有可以借鉴的低本底水泥研发与生产的经验或专利技术材料,其稳定生产存在较大的控制难度。
近期锦屏大设施建设中,原锦屏地下实验室一期项目的低本底水泥生产厂按照原配方和控制经验生产出的水泥无法满足“超净低本底地下实验室”要求,再次证明了低本底水泥的稳定制备尚无成熟、可重复的经验,需要进一步的研究探索。
发明内容
本发明针对以上问题,提供了一种工艺稳定性高,能满足抗辐射性能的低本底水泥的制备方法及低本底水泥。
本发明的技术方案,按照以下步骤进行:
1)、将低本底水泥晶种、C4AF晶须与高镁生料均匀混合后,于1400~1500℃条件下煅烧制得低本底熟料;其中所述的低本底水泥晶种掺量为总质量的1.0~5.0%,C4AF晶须掺量为总质量的1.0~5.0%,高镁生料掺量为剩余量;
2)、将低本底熟料与石膏共同粉磨至比表面积320~360m2/kg,制得低本底水泥。
所述低本底水泥晶种为高镁中热熟料,其Ra-226放射性核素比活度控制在50Bq/kg以内,熟料中MgO含量控制在4.0%~5.0%,50%≤C3S≤55.0%。
所述C4AF晶须中0.3%≤游离氧化钙≤2.0%,尺寸控制在直径0.1~0.3mm,长度5.0mm~30.0mm,其Ra-226放射性核素比活度控制在50Bq/kg以内。
所述的高镁生料中MgO含量控制在2.5%~3.0%,其Ra-226放射性核素比活度控制在40Bq/kg以内。
所述的石膏为天然二水石膏或脱硫石膏,其Ra-226放射性核素比活度控制在50Bq/kg以内。
步骤1)中所用的燃料为低本底煤粉,其Ra-226放射性核素比活度控制在50Bq/kg以内。
步骤2)中所述的低本底熟料与石膏质量百分比为92.0~98.0%:2.0~8.0%。
一种低本底水泥,通过权利要求1所述的方法制备而成。
基于“超净低本底地下实验室”对低本底水泥的迫切需求,结合现有低本底水泥制备过程中烧成困难、放射性核素比活度异常波动大等问题。本发明提供了一种低本底水泥及其制备方法,支撑“超净低本底地下实验室”建设。为实现上述目标,本发明首先提供了一种低本底熟料的稳定制备方法,其由低本底水泥晶种、C4AF晶须与高镁生料均匀混合后,于1400~1500℃条件下煅烧制得。
申请人研究发现,MgO含量的材料相对MgO含量较低的材料放射性活度较低,因此本发明将高镁中热熟料作为低本底水泥晶种,其MgO含量4.0%~5.0%,C3S≤55.0%;同时采取高MgO配比的高镁生料,MgO含量控制在2.5%~3.0%。
C4AF被广泛认为可以提升水泥基材料的抗折强度、韧性,同时Fe等重元素在辐射屏蔽方面具备一定优势,因此基于晶核成形理论,为促进低本底熟料中C4AF的快速烧成、结晶,引入C4AF晶须。
其次,低本底水泥的制备应涉及全过程质量控制,因此本发明对各个原材料的放射性核素比活度均提出具体限制范围,包括入窑煤粉和石膏等,旨在降低低本底水泥的制备和控制难度,提高低本底水泥的放射性核素比活度的稳定性。
本发明一方面基于晶体成核原理,通过引入低本底水泥晶种和C4AF晶须,可以整体降低低本底熟料的烧成难度与能耗,并促进熟料中的铁相固溶体以晶须状的形态定向生成,提升熟料水化产物的增韧效果和对射线的屏蔽吸收效应。
本发明明确了不同原材料的放射性核素比活度,可以通过对低本底的原材料的控制、限定来进一步实现低本底水泥的稳定制备。
附图说明
图1为本发明低本底水泥的制备流程图。
具体实施方式
本发明按照以下步骤进行:如图1所示,
1)、将低本底水泥晶种、C4AF晶须与高镁生料均匀混合后,于1400~1500℃条件下煅烧制得低本底熟料;其中所述的低本底水泥晶种掺量为总质量的1.0~5.0%,C4AF晶须掺量为总质量的1.0~5.0%,高镁生料掺量为剩余量;
2)、将低本底熟料与石膏共同粉磨至比表面积320~360m2/kg,制得低本底水泥。
低本底水泥晶种为高镁中热熟料,其Ra-226放射性核素比活度控制在50Bq/kg以内,熟料中MgO含量控制在4.0%~5.0%,50%≤C3S≤55.0%。
C4AF晶须中0.3%≤游离氧化钙≤2.0%,尺寸控制在直径0.1~0.3mm,长度5.0mm~30.0mm,其Ra-226放射性核素比活度控制在50Bq/kg以内。
高镁生料中MgO含量控制在2.5%~3.0%,其Ra-226放射性核素比活度控制在40Bq/kg以内。
石膏为天然二水石膏或脱硫石膏,其Ra-226放射性核素比活度控制在50Bq/kg以内。
步骤1)中所用的燃料为低本底煤粉,其Ra-226放射性核素比活度控制在50Bq/kg以内。
步骤2)中所述的低本底熟料与石膏质量百分比为92.0~98.0%:2.0~8.0%。
一种低本底水泥,通过本发明的前述方法制备而成。
以下结合具体实施例,对本发明作进一步描述。显然,不能因此将本发明限制在所述的实施例范围之中。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动的前提下所获得的所有其他实施例,均应属于本发明的保护范围。
实施例1
一种低本底水泥的制备方法。将掺量为1%的低本底水泥晶种、1%的C4AF晶须和98%的高镁生料均匀混合后,于1400℃条件下煅烧制得低本底熟料。其中低本底水泥晶种,熟料中MgO含量:4.0%,C3S:53.0%;C4AF晶须中游离氧化钙:0.7%,尺寸:0.1mm,长度5.0mm;高镁生料中MgO含量:2.5%。然后,按质量百分比:低本底熟料92%,石膏8%粉磨制得低本底水泥。本实施例的低本底水泥原燃材料核素含量如表1所示。本实施例的低本底水泥物理性能及核素(Ra-226)含量如表2所示。
实施例2
一种低本底水泥的制备方法。将掺量为2%的低本底水泥晶种、3%的C4AF晶须和95%的高镁生料均匀混合后,于1450℃条件下煅烧制得低本底熟料。其中低本底水泥晶种,熟料中MgO含量:4.5%,C3S:52.0%;C4AF晶须中游离氧化钙:0.5%,尺寸:0.2mm,长度20.0mm;高镁生料中MgO含量:2.5%。然后,按质量百分比:低本底熟料95%,石膏5%粉磨制得低本底水泥。本实施例的低本底水泥原燃材料核素含量如表1所示。本实施例的低本底水泥物理性能及核素(Ra-226)含量如表2所示。
实施例3
一种低本底水泥的制备方法。将掺量为3%的低本底水泥晶种、2%的C4AF晶须和95%的高镁生料均匀混合后,于1450℃条件下煅烧制得低本底熟料。其中低本底水泥晶种,熟料中MgO含量:4.5%,C3S:53.0%;C4AF晶须中游离氧化钙:0.6%,尺寸:0.2mm,长度15.0mm;高镁生料中MgO含量:3.0%。然后,按质量百分比:低本底熟料95%,石膏5%粉磨制得低本底水泥。本实施例的低本底水泥原燃材料核素含量如表1所示。本实施例的低本底水泥物理性能及核素(Ra-226)含量如表2所示。
实施例4
一种低本底水泥的制备方法。将掺量为5%的低本底水泥晶种、5%的C4AF晶须和90%的高镁生料均匀混合后,于1500℃条件下煅烧制得低本底熟料。其中低本底水泥晶种,熟料中MgO含量:4.0%,C3S:54.0%;C4AF晶须中游离氧化钙:0.8%,尺寸:0.3mm,长度30.0mm;高镁生料中MgO含量:2.5%。然后,按质量百分比:低本底熟料98%,石膏2%粉磨制得低本底水泥。本实施例的低本底水泥原燃材料核素含量如表1所示。本实施例的低本底水泥物理性能及核素(Ra-226)含量如表2所示。
表1 低本底水泥原燃材料核素(Ra-226)含量(Bq/kg)
表2 实施例低本底水泥物理性能及核素(Ra-226)含量
应当注意的是,以上所述的实施例仅用于解释本发明,并不构成对本发明的任何限制。通过参照典型实施例对本发明进行了描述,但应当理解为其中所用的词语为描述性和解释性词汇,而不是限定性词汇。可以按规定在本发明权利要求的范围内对本发明作出修改,以及在不背离本发明的范围和精神内对本发明进行修订。尽管其中描述的本发明涉及特定的方法、材料和实施例,但是并不意味着本发明限于其中公开的特定例,相反,本发明可扩展至其他所有具有相同功能的方法和应用。
Claims (6)
1.一种低本底水泥的制备方法,其特征在于,按照以下步骤进行:
1)、将低本底水泥晶种、C4AF晶须与高镁生料均匀混合后,于1400~1500℃条件下煅烧制得低本底熟料;其中所述的低本底水泥晶种掺量为总质量的1.0~5.0%,C4AF晶须掺量为总质量的1.0~5.0%,高镁生料掺量为剩余量;
2)、将低本底熟料与石膏共同粉磨至比表面积320~360m2/kg,制得低本底水泥;
所述低本底水泥晶种为高镁中热熟料,其Ra-226放射性核素比活度控制在50Bq/kg以内,熟料中MgO含量控制在4.0%~5.0%,50%≤C3S≤55.0%;
所述的高镁生料中MgO含量控制在2.5%~3.0%,其Ra-226放射性核素比活度控制在40Bq/kg以内。
2.根据权利要求1所述的一种低本底水泥的制备方法,其特征在于,所述C4AF晶须中0.3%≤游离氧化钙≤2.0%,尺寸控制在直径0.1~0.3mm,长度5.0mm~30.0mm,其Ra-226放射性核素比活度控制在50Bq/kg以内。
3.根据权利要求1所述的一种低本底水泥的制备方法,其特征在于,所述的石膏为天然二水石膏或脱硫石膏,其Ra-226放射性核素比活度控制在50Bq/kg以内。
4.根据权利要求1所述的一种低本底水泥的制备方法,其特征在于,步骤1)中所用的燃料为低本底煤粉,其Ra-226放射性核素比活度控制在50Bq/kg以内。
5.根据权利要求1所述的一种低本底水泥的制备方法,其特征在于,步骤2)中所述的低本底熟料与石膏质量百分比为92.0~98.0%:2.0~8.0%。
6.一种低本底水泥,其特征在于,通过权利要求1所述的方法制备而成。
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