Consolidation of Fragile Weathered Bone Relics Using Hydroxyapatite Material as Consolidant

doi:10.15541/jim20220729

Abstract

Abstract:

Archaeological weathered bones are usually porous and fragile, easily to warp, crack and crumble. To avoid these relic damages, consolidation technology is badly needed. Here, we explored a new consolidation method for weak bone relics using hydroxyapatite as protectant. Briefly, dispersion of calcium oxide mixed with calcium hydrophosphate in alcohol was used firstly to permeate into the fragile bones as precursor of hydroxyapatite consolidant. Then pure water was used to trigger the reaction between calcium oxide and calcium hydrophosphate, which leads to formation of a continuous phase of hydroxyapatite consolidant. By filling and bridging the pores or fissure inside the fragile bones, hydroxyapatite consolidant can act as a reinforcement material. Effects of the mass ratio of calcium oxide to calcium hydrophosphate (1 : 1, 1 : 3, 1 : 4, 1 : 5, 1 : 6, 1 : 7) and the application ways (brushing, drip infiltration and soaking) on the protective performance were investigated by scanning electron microscope (SEM), energy dispersive spectroscope (EDS), X-ray diffraction (XRD) and characterizations of color difference, weight increment, porosity, density and cohesive strength determination. The results showed that the best consolidation performance could be obtained when the mass ratio of 1 : 3 and the brushing consolidation method were adopted. In this case, porosity of the fragile bones decreased by 17.3%. Mass, density and cohesive strength of the fragile bones increased by 38.39%, 34.49% and 16.32%, respectively. Moreover, the color difference of bones is less than 3.0, which is allowable in the field of heritage conservation.

Key words: fragile archaeological bone, consolidation, consolidant, consolidation way, hydroxyapatite

CLC Number:

LIU Yan, ZHANG Yufan, WANG Ximan, LI Ting, MA Wenting, YANG Fuwei, CHEN Liang, ZHAO Dongyue, YAN Xiaoqin. Consolidation of Fragile Weathered Bone Relics Using Hydroxyapatite Material as Consolidant[J]. Journal of Inorganic Materials, 2023, 38(11): 1345-1354.

Figures/Tables 18

Fig. 1 Calcium oxide-calcium hydrogen phosphate dispersion in alcohol at concentration of 25%

Table 1 Experimental groups of different mass ratios

Group	Mass ratio
Group	1 : 1	1 : 3	1 : 4	1 : 5	1 : 6	1 : 7
Brushing	1	2	3	4	5	6
Soaking	7	8	9	10	11	12
Dripping	13	14	15	16	17	18

Fig. 2 Consolidation mechanism of weathered bones using calcium oxide-calcium hydrogen phosphate dispersion in alcohol as consolidant

Fig. 3 Color difference of fragile bone samples after consolidation treatment Samples 1 to 19 are introduced in Table 1, respectively

Fig. 4 Effects of consolidation way and consolidant ratio on the bone weight increment (The rectangle is Interquartile Range (IQR), which is used to mark data outliers) (a) Consolidation way; (b) Consolidant ratio

Fig. 5 Effects of consolidation way and consolidant ratio on the bone porosity (a) Consolidation way; (b) Consolidant ratio

Fig. 6 Effects of consolidation way and consolidant ratio on the bone density (a) Consolidation way; (b) Consolidant ratio

Fig. 7 Effects of consolidation method and consolidant ratio on surface strength of the bones (a) Consolidation way; (b) Consolidant ratio

Fig. 8 Morphology of fragile bone sample before consolidation treatment The areas in red-framed indicate the fractures

Fig. 9 Morphologies of fragile bone samples after consolidation treatments with mass ratios of calcium oxide to calcium hydrogen phosphate at 1 : 1 (a), 1 : 3 (b), 1 : 4 (c), 1 : 5 (d), 1 : 6 (e) and 1 : 7 (f), respectively

Fig. 10 EDS analysis results of fragile bone samples before and after consolidation treatment (a, d) Ca; (b, e) P; (c, f) C, corresponding to Fig. 8 and Fig. 9(b)

Table. 2 EDS analysis results of frgile bone before and after consolidation treatment

Element	Weight ratio before consolidation/%	Weight ratio after consolidation/%
C	0	5.62
O	56.93	56.32
Na	9.57	2.56
Mg	0.91	1.12
P	12.04	13.23
Ca	20.55	21.15
Total	100.00	100.00

Fig. 11 Cross-sectional topographies of fragile bone samples before and after consolidation treatments (a) Untreated; (b-d) Treated by brushing, soaking and dripping, respectively

Fig. 12 Cross-sectional topographies of fragile bone samples treated by different mass ratios of calcium oxide to calcium hydrogen phosphate (a) 1 : 1; (b) 1 : 3; (c) 1 : 4; (d) 1 : 5; (e) 1 : 6; (f) 1 : 7

Fig. 13 XRD results of bones before (a) and after (b) consolidation treatment

Fig. 14 Effect of consolidant ratio on final product Ratios of calcium oxide to calcium hydrogen phosphate in line(a-f) are 1 : 1, 1 : 3, 1 : 4, 1 : 5, 1 : 6 and 1 : 7, respectively

Table 3 Phases of produts under different consolidant ratios

Ratio of CaO : CaHPO₄	Ca(OH)₂	CaHPO₄	Ca₅(PO)₄OH
1 : 1	+++	-	++
1 : 3	-	-	++++
1 : 4	-	++	+++
1 : 5	-	+++	++
1 : 6	-	+++	+
1 : 7	-	++++	+

Fig. 15 Photos of archaeological bone before (a) and after (b) consolidation treatment

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