The Technological Analysis of the Ancient Ceramics Discovered from 'Nanhai No.1 Shipwreck'
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摘要:
“南海Ⅰ号”沉船位于我国广东省阳江市,出水大量陶瓷器的产地研究及腐蚀产物研究是“南海Ⅰ号”研究的重要课题。本文利用微聚焦X射线荧光谱仪(μ-XRF)对“南海Ⅰ号”沉船出水部分的青白瓷、青瓷、绿釉陶的胎釉以及绿釉陶的腐蚀物进行成分分析,并利用体视显微镜以及拉曼光谱仪对绿釉陶表面的腐蚀物进行观察和物相组成分析。元素分析结果表明:一类青白瓷样品胎体具有低铝高硅的特点(Al2O3含量低于19%,SiO2含量约73%),属江西景德镇湖田窑,而另一类青白瓷可能产自福建,具体窑口的确定还有待进一步对比分析才能得出明确的结论;青瓷样品胎体具有高硅低铝的特点(Al2O3含量13.32%~19.12%;SiO2含量72.89%~78.30%),属浙江龙泉窑;绿釉陶样品的特征与福建地区瓷土较为符合,可能来自于福建磁灶窑。拉曼光谱物相分析结果表明,绿釉陶的主要腐蚀物的矿物组成为炭黑、白铅矿与磷酸铅。此项研究成果为出水陶瓷器的产地研究、陶瓷器腐蚀机理探究、出水陶瓷器保护等提供了重要依据。
Abstract:Nanhai No.1 Shipwreck' was discovered in Yangjiang City, Guangdong Province. Research on the origins of these out-water ceramics and corrosion products of ceramics play an important role. The component analysis of body and glaze of bluish-white porcelains, celadons, green glazed potteries and the corrosion products specimens of green glazed potteries have been studied by using Micro-focus X-ray Fluorescence Spectrometer (μ-XRF). Then, the observation and phase analysis of corrosion products specimens of green glazed potteries were conducted by using Stereo Microscope (OM) and Raman Spectroscopy (μ-RS). Combined with ceramic archaeological literature, it ws found that: (1) some bluish-white porcelains are characterized by low content of aluminum and high content of silicon (content of Al2O3 is less than 19%, content of SiO2 is almost 73%), which come from Jingdezhen Hutian kiln; another bluish-white porcelain may be from Fujian Province, which needs further support evidence. (2) The celadons all have a high content of silicon and low content of aluminum (Al2O3: 13.32%-19.12%; SiO2: 72.89%-78.30%), which come from Zhejiang Longquan kiln; additionally, some celadons belong to lime glaze which possess more similar characteristics to Longquan kiln of the Northern Song Dynasty; some belong to lime alkaline glaze which possess similar characteristics to Longquan kiln of Southern Song Dynasty. (3) Green glazed pottery samples possess more similar characteristics to the Fujian area, which may come from Fujian CiZao kiln; in order to have in-depth research on corrosion products of green glazed potteries, representative samples are selected to have Raman spectroscopy analysis; the main compositions are black carbon, cerusite and lead phosphate. In this work, technology analysis has been carried out with some underwater ceramic of 'Nanhai No.1 Shipwreck' to identify some origins of ceramics. The results of this study provide an important basis for the study of the origin of the out-water ceramics, corrosion mechanism of ceramics, ceramic water protection of out-water ceramics amongst other aspects of ceramic origin determination.
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表 1 标本外观描述
Table 1. The exterior appearance of each sample
标本编号 标本种类 外观描述 N1 青白瓷 表面刻花,釉色白中泛青灰;瓷胎较厚,胎灰白 N2 青白瓷 表面刻花,釉色白中泛青灰;瓷胎较厚,胎灰白 N3 青白瓷 表面印花,芒口,釉白中泛青,薄胎,胎洁白细腻 N4 青白瓷 釉色白中泛青,有弦文,胎较薄,洁白细腻 N7 青白瓷 花口,薄胎,釉色白中泛青,胎色洁白细腻 N22 青白瓷 口沿部分,釉色白中泛青,薄胎,胎质洁白 N12 青瓷 口沿及器壁部分,釉色青中发黄,器表划花,灰胎 N13 青瓷 口沿及器壁部分,釉色青中泛白,灰胎 N20 青瓷 器底部分,玉环圈足,釉色深青,器表划花,青灰胎 N5 绿釉陶 绿釉小罐,上面有土黄色,以及黑色斑点状的腐蚀 N8 绿釉陶 器底部分,灰胎,绿釉,表面附着灰色、黑色腐蚀物 N9 绿釉陶 口沿部分,印花,绿釉,表面附着灰色腐蚀物 N10 绿釉陶 口沿部分,印花,腐蚀物较少,但釉表面开始酥粉
N11绿釉陶 器底部分,绿釉,底部内标印花,
灰色腐蚀物,绿釉开始酥粉N16 绿釉陶 小瓶,口颈部分缺失,绿釉,表面锈蚀物很多 表 2 样品胎釉的XRF元素分析结果
Table 2. Elemental compositions of each sample by XRF
样品编号 含量(%) Al2O3 SiO2 TFe2O3 TiO2 MgO CaO Na2O K2O Cr Cu Mn P Rb Sr Zr Zn N1(胎) 21.00 72.30 0.85 0.16 0.25 0.22 1.67 2.55 19 72 277 277 193 62 254 131 N2(胎) 20.37 73.63 1.02 0.16 0.04 0.23 0.93 2.63 17 83 270 242 216 69 284 112 N3(胎) 17.85 73.57 0.55 0.12 0.69 0.91 2.39 2.92 - 0 309 271 381 67 85 68 N4(胎) 18.91 73.84 0.43 0.15 0.60 0.31 1.61 3.14 32 38 232 197 208 61 254 59 N7(胎) 19.00 73.29 0.92 0.15 0.66 0.45 1.86 2.68 11 21 582 272 411 62 130 28 N22(胎) 22.32 70.02 0.78 0.16 0.34 0.31 1.08 4.00 60 71 257 251 310 73 360 158 N1(釉) 14.89 66.50 0.79 0.13 0.63 12.78 0.91 2.37 - 14 1096 993 164 242 228 67 N2(釉) 17.50 67.72 0.72 0.15 0.28 9.28 0.75 2.58 - 28 692 639 164 170 240 78 N3(釉) 14.19 66.37 0.83 0.13 0.43 14.02 0.97 2.05 - 2 455 708 263 209 111 119 N4(釉) 17.61 65.67 0.30 0.13 0.43 10.58 0.84 3.44 - - 748 611 161 186 223 65 N7(釉) 13.85 70.18 0.61 0.13 0.01 8.56 1.74 3.92 15 8 738 723 396 194 88 21 N22(釉) 17.87 64.64 0.72 0.13 1.03 9.36 0.86 4.41 - - 703 1020 224 167 252 96 N12(胎) 15.45 75.59 2.08 0.53 0.04 0.21 1.75 3.35 97 7 292 210 308 53 247 91 N13(胎) 19.12 72.89 1.65 0.26 0.55 0.19 1.75 2.60 34 8 304 253 160 68 173 27 N20(胎) 13.32 78.30 1.73 0.45 0.70 0.24 1.36 2.90 130 37 460 232 245 65 302 95 N12(釉) 12.01 67.88 1.29 0.31 1.67 12.34 0.95 2.54 - - 2716 1498 202 376 273 154 N13(釉) 15.85 71.58 0.74 0.24 1.13 4.38 0.71 4.38 - 43 2395 1265 201 222 172 173 N20(釉) 12.35 61.89 1.24 0.28 2.38 16.28 1.57 3.01 - 26 2437 2875 187 719 269 162 N5(胎) 23.20 65.76 2.32 0.66 1.08 0.32 2.65 3.00 19 162 386 215 206 129 286 149 N8(胎灰色) 26.81 63.28 2.06 0.88 0.73 0.29 1.58 3.39 42 36 557 388 207 104 238 65 N8(胎) 23.91 65.71 1.84 0.70 0.91 0.32 2.35 3.27 56 47 449 288 212 94 297 116 N9(胎) 23.46 65.44 2.30 0.66 1.28 0.48 2.53 2.85 34 284 489 347 176 141 266 100 N10(胎) 21.82 67.29 2.49 0.63 1.46 0.31 2.53 2.47 41 97 458 279 184 99 212 102 N11(胎) 24.57 65.37 2.50 0.70 0.85 0.38 1.57 3.04 25 16 476 274 223 151 237 132 N16(胎) 24.23 65.27 2.45 0.67 1.03 0.36 2.00 2.99 37 135 589 378 192 110 321 92 注:分析结果中,主量成分含量单位为%,微量成分含量单位为μg/g,“-”表示此元素未检出。 表 3 釉陶腐蚀物以及釉陶的半定量分析结果
Table 3. The surface corrosion of green glazed pottery and results of semi-quantitative analysis
样品编号 含量(%) MgO Al 2O 3 SiO 2 P 2O 5 K 2O CaO TiO 2 Fe 2O 3 CoO CuO PbO N5 (白色腐蚀物) - 0.47 2.97 0.24 0.15 0.35 0.08 1.41 0.05 1.07 93.2 N8 (黑色腐蚀物) - 0.43 3.16 0.66 0 0.77 0.11 2.54 0.1 2 90.23 N8 (釉) 1.46 3.15 23.78 0.63 0.61 0.22 0.21 0.52 0.12 5.02 64.28 N8 (灰色腐蚀物) 0.47 19.16 48.21 0.09 6.03 0.2 0.31 2.18 0 0.94 22.42 N8 (黄色腐蚀物) - 8.24 29.87 0.54 3.62 0.77 0.88 5.15 0.13 1.36 47.44 N9 (腐蚀物) - 2.33 19.68 0.52 0.51 0.27 0.18 1.62 0.06 0.85 73.98 N9 (绿釉) 0.6 3.43 21.58 0.48 1.01 0.39 0.11 0.67 0.09 2.66 68.98 N10 (绿釉) 0.42 4.02 40.53 0.25 0.8 0.65 0.22 0.56 0 2.53 50.01 N10(酥粉部分) 0.53 2.62 54.75 0.23 0.82 0.67 0.17 0.49 0.03 1.49 38.2 N10 (黄色腐蚀物) 1.88 8 25.52 4.98 2.45 3.14 0.43 3.48 0.04 1.6 48.48 N11绿釉 1.16 5.22 31.99 0.52 1.43 0.78 0.32 1.16 0.08 3.25 54.09 N11 (灰色腐蚀物) 0.68 3.63 43.74 - 0.63 0.85 0.13 1.22 0.08 1.71 47.34 N16黑色腐蚀物 0.71 1 3.07 0.81 1.13 1.22 0.11 1.26 0.05 2.12 88.3 N16绿釉 0 3.49 26.38 0.27 0.8 0.59 0.13 1.05 0.12 2.38 64.79 N16灰色腐蚀物 0.68 0.74 2.83 0.64 0.5 0.42 0.09 0.91 0 1.17 91.45 注:“-”表示此元素未检出。 -
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