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羟基磷灰石材料在文物保护中的应用述评

  • 杨富巍1,2

    机 构：

    1. 西北大学文化遗产学院文物保护技术系,陕西西安 710069

    2. 文物研究与保护技术教育部重点实验室(西北大学),陕西西安 710069

    ×
  • ， 刘妍1,2

    机 构：

    1. 西北大学文化遗产学院文物保护技术系,陕西西安 710069

    2. 文物研究与保护技术教育部重点实验室(西北大学),陕西西安 710069

    ×
  • ， 张坤1,2

    机 构：

    1. 西北大学文化遗产学院文物保护技术系,陕西西安 710069

    2. 文物研究与保护技术教育部重点实验室(西北大学),陕西西安 710069

    ×
  • ， 周伟强1,2

    机 构：

    1. 西北大学文化遗产学院文物保护技术系,陕西西安 710069

    2. 文物研究与保护技术教育部重点实验室(西北大学),陕西西安 710069

    ×
  • ， 张秉坚3

    机 构：

    3. 浙江大学文物与博物馆学系,浙江杭州 310007

    ×

1. 西北大学文化遗产学院文物保护技术系,陕西西安 710069；
2. 文物研究与保护技术教育部重点实验室(西北大学),陕西西安 710069；
3. 浙江大学文物与博物馆学系,浙江杭州 310007；

Review of research on hydroxyapatite materials used in the conservation of cultural heritage objects

  • YANG Fuwei1,2

    Affiliation：

    1. Department of Preservation Technology for Cultural heritage, School of Cultural Heritage, Northwest University, Xi’an 710069 , China

    2. Key Laboratory for the Preservation and Conservation of Cultural Heritage (Northwest University), Ministry of Education, Xi’an 710069 , China

    ×
  • ， LIU Yan1,2

    Affiliation：

    1. Department of Preservation Technology for Cultural heritage, School of Cultural Heritage, Northwest University, Xi’an 710069 , China

    2. Key Laboratory for the Preservation and Conservation of Cultural Heritage (Northwest University), Ministry of Education, Xi’an 710069 , China

    ×
  • ， ZHANG Kun1,2

    Affiliation：

    1. Department of Preservation Technology for Cultural heritage, School of Cultural Heritage, Northwest University, Xi’an 710069 , China

    2. Key Laboratory for the Preservation and Conservation of Cultural Heritage (Northwest University), Ministry of Education, Xi’an 710069 , China

    ×
  • ， ZHOU Weiqiang1,2

    Affiliation：

    1. Department of Preservation Technology for Cultural heritage, School of Cultural Heritage, Northwest University, Xi’an 710069 , China

    2. Key Laboratory for the Preservation and Conservation of Cultural Heritage (Northwest University), Ministry of Education, Xi’an 710069 , China

    ×
  • ， ZHANG Bingjian3

    Affiliation：

    3. Department of Cultural Heritage and Museology, Zhejiang University, Hangzhou 310007 , China

    ×

1. Department of Preservation Technology for Cultural heritage, School of Cultural Heritage, Northwest University, Xi’an 710069 , China；
2. Key Laboratory for the Preservation and Conservation of Cultural Heritage (Northwest University), Ministry of Education, Xi’an 710069 , China；
3. Department of Cultural Heritage and Museology, Zhejiang University, Hangzhou 310007 , China；

作者简介:

杨富巍(1976—),男,教授,博士,西北大学文化遗产学院文物保护技术系,E-mail:yangfuwei@nwu.edu.cn

中图分类号:K876

文献标识码:A

文章编号:1005-1538(2021)02-0105-05

DOI:10.16334/j.cnki.cn31-1652/k.20200401722

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目录contents

    摘要

    作为一种新兴无机材料,羟基磷灰石近年来在石灰岩、钙质砂岩和甲骨等文物的保护领域得到了广泛的研究和应用。本研究就羟基磷灰石材料本身的特点、保护原理及应用研究现状进行了阐释与评述,指出了其借鉴意义,并展望了羟基磷灰石保护材料研究的发展方向。

    Abstract

    As a kind of emerging protective material, hydroxyapatite has been widely studied and applied in the conservation of limestone, calcareous sandstone and bone relics. In this paper, the characteristics of hydroxyapatite are described, and the application and mechanism of conservation of apatite are introduced. Significant references and the directions of development of hydroxyapatite protective materials are also discussed.

  • 0 引言

  • 羟基磷灰石,又称羟磷灰石,其化学式通常写作Ca5(PO4)3OH。羟基磷灰石化学性质稳定。在自然界,其他钙磷酸盐矿物都有自发转变为羟基磷灰石的趋势[1]。羟基磷灰石的Ksp为2.5×10-59,其溶解度极低,基本可以看作不溶物质,不会因自然降水而发生溶蚀[2]。羟基磷灰石还具有良好的耐酸性,其在pH>4.0的环境中可以稳定存在[3]。该性质可使其免遭空气中二氧化碳、硫氧化物和氮氧化物等酸性污染物的侵蚀。另外,羟基磷灰石还具有适中的力学强度和良好的胶结性能[4]。羟基磷灰石的上述性质使之具有成为文物保护材料的天然优势。近年来,羟基磷灰石材料逐渐引起了文物保护工作者的注意,并开始在大理石、石灰岩、钙质砂岩和甲骨等多种文物的加固保护中得到越来越多的研究和应用。本文将对羟基磷灰石材料的保护原理及其应用研究现状进行简要阐释与评述。

  • 1 保护原理

  • 在研究及保护实践中,通常的做法是将作为羟基磷灰石前驱体材料的钙、磷源先后引入待加固文物,利用钙、磷源之间或钙、磷源与文物基底(主要是大理石、石灰岩等碳酸盐岩类石质文物)的反应生成具有加固保护作用的羟基磷灰石矿物。

  • 其中纳米氢氧化钙是常用的钙源,磷酸(氢)铵等可溶性磷酸盐则是常用的磷源。在对文物进行加固保护处理时,先将纳米氢氧化钙超声分散于低碳挥发性醇溶剂(如甲醇、乙醇、丙醇和丁醇),制成其悬浮液,然后利用表面渗透的方法将此悬浮液引入疏松多孔的待加固文物内部。待溶剂挥发殆尽后,再利用磷酸(氢)铵溶液对待加固文物进行二次渗透处理。经过两次渗透及一定时间的保湿养护处理后,引入的钙、磷源即可反应生成羟基磷灰石矿物,并起到加固保护作用。其中涉及的化学反应如下:

  • 5Ca(OH)2+3NH43PO4⟶Ca5PO43OH+9NH3+9H2O
    (1)

  • 当然,引入的磷酸盐也可以与文物表面层的碳酸钙发生作用而生成羟基磷灰石,其实质为化学转化反应:

  • 5CaCO3+3NH43PO4+H2O⟶Ca5PO43OH+9NH3+5CO2
    (2)

  • 利用上述原理得到的羟基磷灰石矿物可用于风化大理石、石灰岩、钙质砂岩和甲骨等文物的整体加固及表面防护处理。

  • 1.1 风化石灰岩类文物的加固保护

  • 浙江大学张秉坚教授课题组[5]较早地开展了将羟基磷灰石材料用于风化石灰岩类文物保护的研究。在其研究中,先利用表面渗透的方法将钙源纳米石灰(氢氧化钙)的醇悬浮分散液引入待加固的风化灰岩。引入的纳米石灰能将风化石灰岩碎块之间的裂缝和孔洞填塞,并可与空气中二氧化碳反应并最终生成颗粒状的碳酸钙。不过,这些孤立、松散的碳酸钙颗粒只能起到填充作用,而没有实质性的加固效果。

  • 当继续用磷酸铵(TAP)溶液进行二次渗透处理后,一种多孔的羟基磷灰石连续相生成了。它将前面引入的钙源和破碎的风化石块重新结合在了一起。因而,这种钙、磷双补的方法可以在疏松多孔的风化文物内部生成足够多的羟基磷灰石新物相,并借此实现加固的目的。

  • 其实,在处理高密度的大理石、石灰岩和钙质砂岩类文物时,只用磷酸(氢)铵溶液也能起到较好的加固作用,但其中氮、磷营养元素的存在有诱发微生物滋生的危险,需要与抑菌剂配合使用[6]。如普林斯顿大学George Scherer教授课题组[7]利用浸泡法研究了磷酸氢铵(DAHP)、磷酸二氢铵(ADHP)对生物屑石灰岩(bioclastic limestone)的加固效果,并与草酸铵(DAO)加固剂进行了比较。研究结果表明,经草酸铵溶液加固处理后,试样在0~2mm深度的抗钻强度为41.4±2.8N,在0~10mm深度抗钻强则为37.2±3.0N。这表明草酸铵的加固效果内外不均匀,存在表面结壳现象。经磷酸氢铵溶液加固处理后,试样在0~2mm深度加固强度为38.8±5.6N,在0~10mm深度加固强则为37.3±6.2N;经磷酸二氢铵溶液加固处理后,试样在0~2mm深度加固强度为41.1±3.5N,在0~10mm深度加固强则为40.3±3.4N。说明磷酸氢铵和磷酸二氢铵的加固效果更显著,且更均匀。上述处理的效果来自于石灰岩基底中的碳酸钙与引入的草酸盐或磷酸盐之间的化学反应:

  • CaCO3+NH42C2O4⟶CaC2O4⋅H2O+CO2+2NH3
    (3)
  • 5CaCO3+3NH42HPO4⟶Ca5PO43OH+5CO2+6NH3+4H2O
    (4)
  • Ca5PO43OH+5CO2+3NH3+4H2O
    (5)

  • Sassoni等[8-9]研究了浸泡和表面刷涂两种处理方式对风化印第安纳石灰岩加固效果的影响。这种印第安纳石灰岩的孔隙率约为14%,其中方解石的含量超过97%,碳酸镁、氧化硅和氧化铝等的含量合计不足3%。研究结果表明,两种加固方式都有明显的加固效果。当磷酸氢铵(DAHP)溶液的浓度为1.0mol/L时,表面刷涂法可使风化石灰岩的毛细水吸收降低26%,弹性模量增加71.1%,抗压强度增加17.5%。浸泡法的效果则更胜一筹,它可使风化石灰岩的毛细水吸收降低约44%,弹性模量增加96%,抗压强度增加25.5%。Ma等[10]将磷酸氢铵溶液用于塞浦路斯一处石灰岩墓葬的保护处理并得到了较为满意的结果。研究发现,经磷酸氢铵溶液渗透处理后,风化石灰岩表面的方解石颗粒即转化为网状结构的羟基磷灰石矿物,并与石灰岩基底重新结合起来,粉化脆弱的石灰岩石壁也因而得到了加固保护。Naidu等[11]的研究表明,将磷酸氢铵溶液与氯化钙配合使用可显著提高加固效果,能使加固强度提高23.4%以上。这与钙离子引入后石灰岩的溶解被抑制且在其孔隙中生成更多的羟基磷灰石矿物有关。Sassoni等[12-13]的研究表明,以磷酸氢铵为加固剂时,作为额外的补钙材料,石灰(氢氧化钙)水比氯化钙对加固强度的提高更为明显。这应该与碱性条件有利于羟基磷灰石的生成有关。此外,与商业有机硅(ES)材料相比,羟基磷灰石材料还具有强度形成迅速,加固强度适中,兼容性好和安全可靠等优点[14]。

  • 1.2 钙质砂岩的加固保护

  • 从2012年开始,Yang等[15]还尝试将钙、磷双补的方法用于加固风化钙质砂岩。其所用砂岩试样中碳酸钙含量为10%,与云冈石窟钙质胶结砂岩中碳酸钙含量相当。研究结果表明,经纳米氢氧化钙的醇悬浮液和磷酸铵溶液渗透处理后,风化砂岩的毛细水吸收和透气性基本维持不变,而抗压强度则提高了近5倍,体现了良好的兼容性和加固效果。Sassoni等[16]随后利用类似方法对意大利两种风化钙质砂岩(锡耶纳黄泥岩(GS)和塞茵那石(PS),其中碳酸钙含量分别为84.3%和12.8%)进行了加固保护试验,也得到了较为满意的结果。之后,Franzoni等[17-18]还比较了表面刷涂、敷贴和浸泡等三种不同使用方式下磷酸氢铵溶液的保护效果。结果表明:表面刷涂法对风化岩石试块强度提高最大,且对石材孔隙结构、透气性和外观的影响最小,更适于石质文物的现场保护。总地来看,钙质胶结砂岩类石质文物适合于用磷酸(氢)铵来保护且含钙量越高,加固效果越好;而磷酸(氢)铵对不含钙质胶结物的砂岩保护效果并不理想,也不推荐单独使用磷酸(氢)铵进行加固处理[19]。

  • 1.3 石灰岩及大理石文物的表面防护

  • 羟基磷灰石材料还可用于大理石和石灰岩等碳酸盐岩类石质文物的表面防护处理。大理石和石灰岩的主要成分是碳酸钙,而碳酸钙的化学性质不够稳定,在空气中二氧化碳、硫氧化物、氮氧化物及水的作用下就会发生溶蚀和风化。在其表面制备具有保护作用的羟基磷灰石膜就可抑制,甚至避免这种现象的发生。

  • Yang等[20-21]的研究表明,以磷酸铵或磷酸二氢钙为转化剂,利用敷贴方法即可在石灰岩的表面形成羟基磷灰石膜。其进一步研究发现利用磷酸盐甚至可以将石灰岩文物表面有害的石膏风化层或沉积层[22]原位转化为羟基磷灰石膜。此种羟基磷灰石转化膜与石质文物的基底为化学结合,物理化学性质稳定,耐溶蚀,可以为其下的文物本体提供良好的保护[23]。Naidu等[24-25]的研究表明,在利用磷酸铵制备羟基磷灰石转化膜时,加入氯化钙和碳酸铵可加速羟基磷灰石膜的生成,降低其孔隙率并提高其耐酸性能。Naidu等[26]还将上述方法制得的羟基磷灰石保护膜与草酸钙保护膜进行了比较,结果发现羟基磷灰石膜的长期保护效果比草酸钙更加优越。这是因为羟基磷灰石比草酸钙的溶解度小得多,不会因发生溶蚀作用而失效。Graziani等[27-28]又对上述制备方法进行了改进,他们通过在磷酸氢铵和氯化钙溶液中加入乙醇的方法使制得的羟基磷灰石保护膜更加致密,对其下石材的表面覆盖更加完整且无开裂现象,耐酸性也优于草酸钙膜。Sassoni等[29]的研究还发现,除了乙醇外,异丙醇也可起到类似作用,而且效果更好。这与醇类添加物表面张力低,有利于减小溶液中离子的水化半径,并使磷酸根与碳酸钙之间的反应更加均匀有关。Xu等[30]的研究发现,将表面活性剂十六烷基三甲基溴化铵(CTAB)加入磷酸氢铵处理液后得到羟基磷灰石膜的结晶度、比表面积和孔尺寸都有明显降低,有利于其耐酸性、结合力等保护性能的提高。

  • 1.4 甲骨类文物的加固

  • 甲骨类文物的无机成分主要是羟基磷灰石,因此利用羟基磷灰石保护甲骨类文物属于“以骨补骨”,加固材料羟基磷灰石与甲骨文物的本体成分一致,兼容性高,更加安全可靠。

  • 刘晓清等[31]将羟基磷灰石粉末分散于胶原溶液中制成胶原-羟基磷灰石复合材料,并将之用于临淄东周墓“殉马坑”骨质文物的加固保护。研究结果表明,经上述复合材料加固保护处理后马骨的力学性能增强,基本无色差,且保护1年后也未出现霉变现象。王恺等[32]将纳米羟基磷灰石溶胶和胶原蛋白溶液混溶后制成复合加固材料,并将之用于龟甲类文物的加固保护。研究表明,该复合材料干燥固结后结构类似于骨,可以在甲骨文物的风化孔洞中形成有效的填充和连接,作为修复材料具有独特的优势。刘林西等[33]以羟基磷灰石粉末和丙烯酸乳液(B60)的混合物为裂隙填充材料,以纳米氢氧化钙和磷酸铵溶液为渗透加固剂,对出土象牙化石进行了有效的保护。Gong等[34]则直接利用纳米羟基磷灰石胶体加固金沙遗址出土的古象牙。研究结果表明,利用上述材料在古象牙表面形成羟基磷灰石保护层后,古象牙的硬度、弹性模量和耐刮擦等力学性能有了显著提高,而其外观可基本维持不变,体现了良好的应用前景。North等[35]研究了磷酸氢铵溶液对骨样的加固保护效果。研究结果表明,磷酸氢铵溶液可以和骨样中的碳酸钙反应生成新的羟基磷灰石矿物而起到加固作用。但骨样中可利用碳酸钙较少,要生成一定量的羟基磷灰石矿物,需要在引入磷酸铵溶液前先引入氢氧化钙或碳酸钙。Yang等[30]则用钙、磷双补方法来保护骨质文物。研究发现,将纳米氢氧化钙和磷酸铵溶液先后引入风化的骨质文物后,氢氧化钙和磷酸铵在常温下即可发生反应,并在风化骨质文物内部生成多孔、相互连接的羟基磷灰石矿物。该羟基磷灰石矿物可以把风化、疏松的骨质文物重新固结起来,而达到良好的保护效果。

  • 2 结语

  • 由于羟基磷灰石材料良好的耐候性和适中的强度,其在风化石灰岩、砂岩和骨质文物的整体加固及表面防护等领域得到了越来越多的研究与应用。其保护原理和研究方法对于新型文物保护材料的研究极具启示和借鉴意义。不过,现有保护方法在制备羟基磷灰石时多采用磷酸(氢)铵为前驱物,其中的氮、磷元素有造成微生物滋生的风险。另外,在用于表面防护时,现有制备方法得到羟基磷灰石膜都是多孔结构,不够致密,制约了其耐候性的提高,仍需进一步改进。相信随着研究工作的持续推进,基于羟基磷灰石材料的文物保护方法将不断发展完善,并最终能在文物保护实践中得到推广使用。

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  • 基本信息

    中图分类号: K876
    文献标识码: A
    DOI: 10.16334/j.cnki.cn31-1652/k.20200401722
    文章编号: 1005-1538(2021)02-0105-05

    基金信息

    引用信息

    稿件历史

    收稿日期: 2020-04-11

  • 参考文献

    • [1] LIU D M,CHOU H M,WU J D.Hydroxyl apatite coating via amorphous calcium phosphate[J].Materials Chemistry and Physics,1994,37(1):39-44.

    • [2] 钱功明,王俊,孙星月,等.Fe3+对羟磷灰石溶解特性的影响[J].矿物学报,2017(增刊1):49-52.QIAN Gongming,WANG Jun,SUN Xingyue,et al.Effect of Fe3+ on dissolution behavior of hydroxyapatite[J].Acta Miner Alogica Sinica,2017(Suppl 1):49-52.

    • [3] 卢娟,梁列峰,翁杰,等.LiCl引入对羟基磷灰石陶瓷耐酸蚀及烧结的影响[J].材料导报,2010(增刊1):395-397.LU Juan,LIANG Liefeng,WENG Jie,et al.Influence of anti acid capability and sintering performance on hydroxyapatite ceramic introduced LiCl[J].Materials Review,2010(Suppl 1):395-397.

    • [4] 王剑龙,何由,程哲,等.自固化磷酸钙骨水泥的制备及其性能评估[J].中国组织工程研究,2018(18):2800-2806.WANG Jianlong,HE You,CHENG Zhe,et al.Preparation and property evaluation of a self-setting calcium phosphate cement[J].Chinese Journal of Tissue Engineering,2018(18):2800-2806.

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