*3.1. Body Phase Identification*

Raman spectra (Figures 6–13) have been recorded on the glaze-free body for the different artifacts (see Figure 6A (R1045), Figure 7A (TH457), Figure 8B (R1175) and Figure 9A,B (R1006 and SN284)). In these spectra, the narrow main peak of quartz (SiO2) was observed at ca. 460 cm−<sup>1</sup> [28,29], shifted down to lower wavenumbers than that of the isolated quartz mineral (~463 cm−<sup>1</sup> ) due to the compressive stress of the glassy matrix on the quartz grains. A broader component at ca. 480 cm−<sup>1</sup> was also observed (see e.g., Figures 7A and 9B), characteristic of a glassy aluminosilicate phase forming the porcelain body in between acicular mullite crystals forming a 3D network [30,31]. The mullite phase was generally not detected with a mobile Raman spectrometer due to the operating conditions of the mobile setup and poor intensity of the mullite Raman spectrum. Only in the body spectrum of the R1045 cup (Figure 6A(a)) could very small features at ~960 and 1130 cm−<sup>1</sup> be considered to come from the mullite phase [28]. The Raman spectrum of the glaze, fired at a high temperature with the porcelain body, was rather similar, but the intensity of the ~490 to 505 cm−<sup>1</sup> broad component was stronger, and the quartz peak was mostly weaker, as observed for the glaze spectra of the R1045 and R1041 cups (Figure 6A(b),C(b)).

*Heritage* **2020**, *3* quartz peak was mostly weaker, as observed for the glaze spectra of the R1045 and R1041 cups (Figure 6A(b),C(b)).

green.

A)

122

460

510

503

460

625

305

460

<sup>600</sup> <sup>288</sup> <sup>400</sup>

435

460

507

390

335

300

195

216

d)

A)

Raman Intensity

130

a)

Raman Intensity

b)

490

502

605

655

775

773

810

**3. Results and Discussion** 

*3.1. Body Phase Identification* 

*Heritage* **2020**, *3* FOR PEER REVIEW 8 of 27

noted the information thickness during the analysis of the enamel was estimated to be ~4 µm at Si

Raman spectra (Figures 6–13) have been recorded on the glaze-free body for the different artifacts (see Figures 6A (R1045), 7A (TH457), 8B (R1175) and 9A,B (R1006 and SN284)). In these spectra, the narrow main peak of quartz (SiO2) was observed at ca. 460 cm−1 [28,29], shifted down to lower wavenumbers than that of the isolated quartz mineral (~463 cm−1) due to the compressive stress of the glassy matrix on the quartz grains. A broader component at ca. 480 cm−1 was also observed (see e.g., Figures 7A and 9B), characteristic of a glassy aluminosilicate phase forming the porcelain body in between acicular mullite crystals forming a 3D network [30,31]. The mullite phase was generally not detected with a mobile Raman spectrometer due to the operating conditions of the mobile setup and poor intensity of the mullite Raman spectrum. Only in the body spectrum of the R1045 cup (Figure 6A(a)) could very small features at ~960 and 1130 cm−1 be considered to come from the mullite phase [28]. The Raman spectrum of the glaze, fired at a high temperature with the porcelain body, was rather similar, but the intensity of the ~490 to 505 cm−1 broad component was stronger, and the

Kα, 130 µm at Cu Kα, 220 µm at Au Lα and ~2.5 mm at Sn Kα [18].

**Figure 6.** Representative Raman spectra recorded on the body, glaze and painted enamels of the porcelains: (**A**) R1045 cup (a) body, (b) white, (c,c') blue; (**B**) R1048 cup (a) white, (b) blue, (c) yellow, (d,d',d'') red, (e,e') black (line); (**C**) R1041 cup (a) blue (flower), (b) colorless glaze, (c) pink; (**D**) R1135 **Figure 6.** Representative Raman spectra recorded on the body, glaze and painted enamels of the porcelains: (**A**) R1045 cup (a) body, (b) white, (c,c') blue; (**B**) R1048 cup (a) white, (b) blue, (c) yellow, (d,d',d") red, (e,e') black (line); (**C**) R1041 cup (a) blue (flower), (b) colorless glaze, (c) pink; (**D**) R1135 cup (a,a',a") blue, (b,b',b") red (eye), (c,c') green areas. *Heritage* **2020**, *3* FOR PEER REVIEW 9 of 27

cup (a,a',a'') blue, (b,b',b'') red (eye), (c,c') green areas.

**Figure 7.** Representative Raman spectra recorded on the body, glaze and painted enamels of the **Figure 7.** Representative Raman spectra recorded on the body, glaze and painted enamels of the TH457 (**A**) and F1371C bottles (**B**): (a,a') white, (b,b') dark blue, (c,c') celadon (green), (d) yellow-green.

TH457 (**A**) and F1371C bottles (**B**): (a,a') white, (b,b') dark blue, (c,c') celadon (green), (d) yellow-

B)

456

320

220 290 400 490

c)

**d**)

a)

b)

B)

131

440

455

456

500

320

c)

515

<sup>780</sup> <sup>495</sup>

600 655

765

c) a")

a')

e')

1565

1305

1345

1565

e")

e') e)

**c**) b) a)

**Figure 8.** Representative Raman spectra recorded on the painted enamels of the R1175 large plate (**A**) (a,a',a'') (marli) yellow, (b) (marli) blue, (c) orange (coat), (d) red (flower), (e,e') (marli) black; and

500 1000 1500

Wavenumber / cm-1

795

810

Wavenumber / cm-1

980

1060

1060

905

810

970

1035

1120

1305

1455 1570 1320

**Figure 9.** Representative Raman spectra recorded on the body, glazes and painted enamels of the R1006 dish (**A**) (a) light yellow, (b) blue glaze, (c) colorless glaze, (d) body, (e,e',e'') black (e' and e'' corresponded to very short counting times, and e, to 500 accumulations); and SN284 pot (**B**) (a,a')

Wavenumber / cm-1 500 1000 1500

**e**) d)

b) a') a)

small plate (**B**) (a) blue, (b) green, (c) red (line), (d) body.

1015

133 d)

Wavenumber / cm-1

500 1000 1500

985

975

1040

yellow, (b) green, (c) red (flower), (d) pink (textile), (e) body.

500 1000 1500

green.

A)

A)

131

131

Raman Intensity

Raman Intensity

0 500 1000 1500

0 500 1000 1500

1073

1073

985

985

1310

1310

paste

paste

white - pink glaze

white - pink glaze

dark yellow

dark yellow

orange **yellow**

orange **yellow**

**yellow**

**yellow**

red

red

blue

blue

475

475

390

455

390

508

508

455

340

340

405

405

602

655

655

602

640

640

780

780

820

820

240

240

292

292

220

220

200

200

**Figure 7.** Representative Raman spectra recorded on the body, glaze and painted enamels of the

**Figure 7.** Representative Raman spectra recorded on the body, glaze and painted enamels of the TH457 (**A**) and F1371C bottles (**B**): (a,a') white, (b,b') dark blue, (c,c') celadon (green), (d) yellow-

Wavenumber / cm-1 500 1000 1500

Wavenumber / cm-1 500 1000 1500

137

137

600

600

670

770

670

813

813

770

1015

Wavenumber / cm-1

Wavenumber / cm-1

Wavenumber / cm-1

a)

a')

1070

1015

1130

1070

1130

1130

1130

1070

1025

1070

1025

1313

1313

1550

1550

c') d) c) b') b) a') a)

c') d) c) b') b) a') a)

1450

1450

420

420

300

300

442

442

492

520

492

540

520

540

335

335

B)

B)

*Heritage* **2020**, *3* FOR PEER REVIEW 9 of 27

*Heritage* **2020**, *3* FOR PEER REVIEW 9 of 27

**Figure 8.** Representative Raman spectra recorded on the painted enamels of the R1175 large plate (**A**) (a,a',a'') (marli) yellow, (b) (marli) blue, (c) orange (coat), (d) red (flower), (e,e') (marli) black; and small plate (**B**) (a) blue, (b) green, (c) red (line), (d) body. **Figure 8.** Representative Raman spectra recorded on the painted enamels of the R1175 large plate (**A**) (a,a',a") (marli) yellow, (b) (marli) blue, (c) orange (coat), (d) red (flower), (e,e') (marli) black; and small plate (**B**) (a) blue, (b) green, (c) red (line), (d) body. **Figure 8.** Representative Raman spectra recorded on the painted enamels of the R1175 large plate (**A**) (a,a',a'') (marli) yellow, (b) (marli) blue, (c) orange (coat), (d) red (flower), (e,e') (marli) black; and small plate (**B**) (a) blue, (b) green, (c) red (line), (d) body.

**Figure 9.** Representative Raman spectra recorded on the body, glazes and painted enamels of the R1006 dish (**A**) (a) light yellow, (b) blue glaze, (c) colorless glaze, (d) body, (e,e',e'') black (e' and e'' corresponded to very short counting times, and e, to 500 accumulations); and SN284 pot (**B**) (a,a') **Figure 9.** Representative Raman spectra recorded on the body, glazes and painted enamels of the R1006 dish (**A**) (a) light yellow, (b) blue glaze, (c) colorless glaze, (d) body, (e,e',e'') black (e' and e'' corresponded to very short counting times, and e, to 500 accumulations); and SN284 pot (**B**) (a,a') **Figure 9.** Representative Raman spectra recorded on the body, glazes and painted enamels of the R1006 dish (**A**) (a) light yellow, (b) blue glaze, (c) colorless glaze, (d) body, (e,e',e") black (e' and e" corresponded to very short counting times, and e, to 500 accumulations); and SN284 pot (**B**) (a,a') yellow, (b) green, (c) red (flower), (d) pink (textile), (e) body. *Heritage* **2020**, *3* FOR PEER REVIEW 10 of 27

**Figure 10.** Representative Raman spectra recorded on the painted enamels of the TH487 plate: (**A**) (a,a') red, (b,b') yellow (cock), (c) (marli) light yellow; (**B**) (a,a') blue, (b) green, (c,c',c'') black (c, very **Figure 10.** Representative Raman spectra recorded on the painted enamels of the TH487 plate: (**A**) (a,a') red, (b,b') yellow (cock), (c) (marli) light yellow; (**B**) (a,a') blue, (b) green, (c,c',c") black (c, very short counting time), (d) red.

short counting time), (d) red.

450

502

520

765 813

461

320

b)

A)

130

Raman Intensity

a')

**Figure 11.** Representative Raman spectra recorded on the glaze and painted enamels of the R1056

Wavenumber / cm-1 0 500 1000 1500

135

B)

490

<sup>970</sup> <sup>910</sup>

Wavenumber / cm-1

tiger plate (**A**) (a,a') white (tiger belly), (b) pink, (c) glaze; and SN284 pot (**B**) yellow.

500 1000 1500

980

1035

*Heritage* **2020**, *3* short counting time), (d) red.

A)

Raman Intensity

327 <sup>440</sup> <sup>133</sup>

**Figure 10.** Representative Raman spectra recorded on the painted enamels of the TH487 plate: (**A**) (a,a') red, (b,b') yellow (cock), (c) (marli) light yellow; (**B**) (a,a') blue, (b) green, (c,c',c'') black (c, very

Wavenumber / cm-1 500 1000 1500

304

1140

glaze

1562

d)

a') a)

c") c')

c)

1336

1071 922

Wavenumber / cm-1

1037 971 915

500 1000 1500

9681045

807

*Heritage* **2020**, *3* FOR PEER REVIEW 10 of 27

B)

b)

813

585

<sup>608</sup> <sup>773</sup> 813

485

1570

c)

a)

b') b)

1325

a')

**Figure 11.** Representative Raman spectra recorded on the glaze and painted enamels of the R1056 **Figure 11.** Representative Raman spectra recorded on the glaze and painted enamels of the R1056 tiger plate (**A**) (a,a') white (tiger belly), (b) pink, (c) glaze; and SN284 pot (**B**) yellow. *Heritage* **2020**, *3* FOR PEER REVIEW 11 of 27

**Figure 12.** Representative Raman spectra recorded on the F1429C teapot for different colored painted enamels: (A) white (a) and blue (b) enamels; (B) dark green (a,a') and yellow (b,b',b'') enamels; (C) **Figure 12.** Representative Raman spectra recorded on the F1429C teapot for different colored painted enamels: (**A**) white (a) and blue (b) enamels; (**B**) dark green (a,a') and yellow (b,b',b") enamels; (**C**) pink (a,a') and red (b,b') enamels; (**D**) brown (a,a') and black (b,b') enamels.

B)

126

Raman Intensity

133

445

460

480

473

340

290

pink (a,a') and red (b,b') enamels; (D) brown (a,a') and black (b,b') enamels.

500 1000 1500

Wavenumber / cm-1

1040

1110

980

970

1035

815

772

813

b')

285

320

437

A)

128

Raman Intensity

b)

500 1000 1500

Wavenumber / cm-1

975

895

813 777

1040

1015

1030

980

a'') a')

c)

c')

c'')

b) a)

a'') a')

a)

**Figure 12.** Representative Raman spectra recorded on the F1429C teapot for different colored painted

*Heritage* **2020**, *3* FOR PEER REVIEW 11 of 27

**Figure 13.** Representative Raman spectra recorded on the painted enamels of the F1341C bottle: (**A**) white (a,a',a''') and blue (b,b'); (**B**) green (a,a',a'' light green) and yellow (b,c,c',c''); (**C**) orange (a) and **Figure 13.** Representative Raman spectra recorded on the painted enamels of the F1341C bottle: (**A**) white (a,a',a"') and blue (b,b'); (**B**) green (a,a',a" light green) and yellow (b,c,c',c"); (**C**) orange (a) and red (b,b').

## red (b,b'). *3.2. Phase Identification in Colored Glaze*/*Enamels*

(Table 2).

**Yellow (overglaze)** 

**Yellow-green** 

**Green** 

*3.2. Phase Identification in Colored Glaze/Enamels*  Different phases were identified by Raman analysis for the different colored areas of the Chinese painted enameled porcelains, such as white, blue, yellow (and green), red (purple to red) and pink Different phases were identified by Raman analysis for the different colored areas of the Chinese painted enameled porcelains, such as white, blue, yellow (and green), red (purple to red) and pink (Table 2).



arsenate

Sb–Sn–(Zn, Fe?) NY pyrochlore + As apatite

As-apatite

R1175, TH457 Sb-rich NY pyrochlore ~122/130, ~335, 508

Sn-rich NY pyrochlore ~130–133, ~455

~133, 327, 440, ~810–820 (broad)

134, 330, 450, 480–490, 518, 810, 770 (sh)

> ~133, 330, 815, 770

Blue type 3 Smalt?

Blue (glaze) R1006 glassy silicate (+ quartz) 460, 503

TH487, R1056 Sn-rich NY pyrochlore +

**(overglaze)** R1135 Sn-rich NY pyrochlore ~130–133, 330, 455

R1175, R1006, R1048, TH487, SN284, R1135

F1429C, F1341C?, TH457

**(overglaze)** R1135 Sn-rich NY pyrochlore +


**Table 2.** *Cont.*
