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To acquiesce array investigation, the sample P3_L was anchored in polyester and adhesive adhesive afore the dry apparent was able with annoying cutting cardboard (for capacity see Supplementary Information). Examination of the cross-sectioned, stratigraphic sample by OM (Fig. 2a,b) and SEM-EDX (Fig. 2c,d and Table 1) appear the advantaged “Laque arrachee” address of the Dunand workshop, which consisted of appropriation the beginning bark with a board spatula to actualize an asperous surface2. This was analogously acclimated for one of the best absorbing interiors accomplished by Dunand in 1928 for the accommodation of Templeton Crocker in San Francisco as able-bodied as for a alternation of aesthetic bank panels advantaged “Les peoples d’Asie et d’Afrigue” fabricated for the 1931 Exposition Coloniale in Paris2. In this case the “Laque arrachee” consists of a black, bunched and constant (≈20 µm thick) bandage (Layer 1) with a bouncing apparent activated on a arena bandage (Layer 0) which alone contains a few small, broadcast ashen grains of silica and feldspar as the asleep apparatus (Fig. 2). The reddish-greyish arena Bandage 0, with an boilerplate array of ≈135 µm, is mostly characterized by adhesive adhesive (CaSO4 • 2H2O – Ca and S in a arrangement ≈1:1). This is arresting in SEM as an accessible cast of hydrated gypsum, as able-bodied as by OM and SEM as dark-brown or ashen un-hydrated particles. Bandage 0 additionally contains anyhow broadcast red grains, arresting by OM and articular by EDX point assay as adamant (Fe). This suggests that Dunand atramentous the arena bandage red in adjustment to burrow the attributes of the white adhesive ingredients, a convenance appear elsewhere16. The atramentous Bandage 1 was followed by the appliance of a constant bandage (Layer 2) with a anemic chicken color, ≈40 µm thick, absolute both of titanium oxide (TiO2) and cartilage white (Ca3(PO4)2) grains.

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How to draw Oil Conservation for better Environment (save fuel) poster – step by step – easy painting on oil conservation | easy painting on oil conservation

(a) Optical microscopy angel of the cross-sectioned sample empiric by reflected arresting ablaze assuming the capital layers as able-bodied as the µATR-FTIR mapped breadth (red box – Section 2.3) and (b) by ultraviolet light. (c) SEM micrograph of the accomplished cross-sectioned sample and (d) detail of the breadth advised by point and aggregate EDX assay assuming the capital bark acrylic layers.

Above this, Bandage 3 is appreciable by arresting ablaze as a aphotic orange bandage (≈25 µm). It is formed by the arsenic-based colorant orpiment (As2S3). Assay of abounding baby orange grains by EDX point analysis, as able-bodied as the bandage aggregate EDX assay of the absolute bandage (shown in Table 1) confirms an As to S arrangement of 2:3, agnate with orpiment. This bandage forth contains a baby abundance of the red colorant vermillion (HgS) apparent by point EDX analysis. Ultraviolet ablaze optical microscopy showed two added actual attenuate apical layers (Fig. 2b), one of which appears atramentous due to the absence of fluorescence (Layer 4) and another, which exhibits able bluish fluorescence (Layer 5). This closing one is acceptable ascribable to a coating/protective layer, which was added advised by µATR-FTIR (Section 2.3). The bandage that appears atramentous beneath UV betterment is composed of gold on the larboard ancillary of the sample and chestnut on the adapted side, arch to the estimation that Dunand acclimated both of these two metals for imparting altered finishing blush furnishings to the acrylic surface. In Fig. 2d, this brownish bandage was alone during sample alertness and appears both aloft and beneath Bandage 5 and accordingly labelled as “folded up Bandage 4”. This sample was taken from an breadth of the console visibly characterized by a bi-metallic appearance, actual acceptable due to the appliance of broadcast or sprayed beautification décor, which is appear abroad as a address that Dunand used, forth with the appliance of gold blade or a brownish finish3. Sugawara additionally accomplished the assimilation of metal leafs and crumb as a beautification address to Dunand during the 1912 bark training session2.

The THM-GC/MS after-effects highlight the circuitous agreement of the altered types of actual that Dunand acclimated for his bark console painting. Firstly and mostly importantly, the attendance of the Vietnamese bark laccol was apparent by the identification and assuming of several adapted Anacardiaceae timberline sap pyrolysis compounds. The ample breadth “gestalt” blueprint apparent in Fig. 3 shows anniversary specific Anacardiaceae timberline sap pyrolysis admixture (e.g.cathecol, acerbic cathecol, alkyl benzene etc.) in one blush by acute the aiguille breadth in the y-axis of the cardinal of carbon atoms and bifold bonds in the x-axis4. Those detected are represented by acerbic catechols, with C10 arlenic acerbic as the best abundant, catechols with a best ancillary alternation breadth of C17 and aliphatic hydrocarbons with C7 as the best acute ones, and a alternation of alkyl benzenes from C3 to C10.

Gestalt blueprint of Anacard markers detected in the advised acrylic sample.

Another adumbration of the attendance of laccol was the apprehension of some carbohydrate compounds (Table 2) basic from gums and glycoproteins. These action artlessly in Anacard saps, and are about three times college in laccol than urushi sap17. They are represented by a accumulation of three compounds eluted at about 1500 RI units with abject aiguille of m/z 129 and accession one begin at 2467 RI units with m/z 88. The aboriginal set was apparently formed during pyrolysis from monosaccharides and uronic acids, while the added one was mainly generated from the pyrolysis of disaccharides4. In accession to laccol, the use of a dehydration oil was adapted by the apprehension of both monocarboxylic (e.g. C16:0 palmitic, C18:1 oleic, C18:0 stearic acids) and dicarboxylic acids (e.g. C8:0 suberic, C9:0 azelaic, C10:0 sebacic acids) as able-bodied as by glycerol, which is apparent by the bar blueprint in Fig. 4. Based on the palmitic to stearic acerbic arrangement P/S of 1.5, linseed oil was articular as the blazon of dehydration oil begin in the acrylic sample.

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Fatty acerbic bar blueprint for the advised acrylic sample.

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Oil Conservation poster (save fuel) drawing for beginners with oil pastel – step by step – easy painting on oil conservation | easy painting on oil conservation

Besides laccol and linseed oil, adapted brand compounds of a diterpenic adhesive such as that from Pinaceae (pine) timberline were additionally detected (Table 2). Those compounds are mainly characterized by dehydroabietic acerbic (DHA)-methyl ester, 6-DHA-methyl ester, 7-methoxy-tetra-DHA-methyl ester, 7-oxo-DHA-methyl ester, and 7,15-dimethoxy-tetra-DHA-methyl ester, which are blaze articles of the capital diterpenic adhesive basic abietic acid. The added apprehension of the mercusic acid-dimethyl ester and the absence of palustric acerbic may announce a ache adhesive acquired from the Pinus latteri species, which is built-in to Southeast Asia including Vietnam as able-bodied as southeast Burma, arctic Thailand, Laos and Cambodia1,18.

Other advice about the circuitous sample agreement was accent by the attendance of some protein analytic markers (1H-pyrrole,1-methyl, pyrrole, 2-aminopyridine, protein 3-blood & glue, and cement marker-Mazzeo) cogent the attendance of beastly cement (Table 2), additionally complemented by the apprehension of dimethyl disulfide and dimethyl sulfate (Table 2), which are frequently produced by sulfur absolute amino acids beneath the analytic altitude active in this study. In accession to Vietnamese bark and the amoebic additives linseed oil and ache resin, the THM-GC/MS investigations on the apical layers of the console painting appear the attendance of shellac, additionally accepted to accept been broadly acclimated by Dunand2. The archetypal hydroxyl aliphatic and terpene acids derivatives of attack such as aleuritic acerbic derivatives, shelloic and laccishelloic acids, as able-bodied as jalaric acids19 were articular (Table 2).

Beyond the identification of amoebic compounds, hints of the attendance of the two asleep pigments orpiment (As2S3) and cartilage white (Ca3(PO4)2) can be acquired from the THM-GC/MS after-effects (Table 2). Arsenic based colorant was apparent by the apprehension of dimethyl-methylthio-arsine (C3H9AsS) pyrolysis artefact and of its pyrolysis artefact As4, while cartilage white was detected by the attendance of trimethyl phosphate, which is frequently formed back cartilage atramentous and the phospholipids in claret and egg are pyrolyzed beneath the altitude acclimated in this study2. These after-effects apropos the asleep pigments acclimated in this appointment accord with the SEM-EDX assay discussed in Section 2.1.

The final footfall of the assay had the ambition of allotment anniversary alone amoebic admixture detected in the acrylic sample by THM-GC/MS, such as the Vietnamese bark and its additives, linseed oil, ache resin, and shellac, to a specific stratigraphic bandage of the able cross-sectioned sample. This appointment is decidedly important for a bigger compassionate of the painting’s stratigraphy, and accordingly the aesthetic address acclimated by Dunand. For this purpose, µATR-FTIR abstracts were performed on a adumbrative sample breadth that included all axiological acrylic layers (red box in Fig. 2a). The all-embracing breadth of assay corresponded to 145 × 135 μm2, with 10 × 10 credibility of measurements, constant in a absolute of 100 spectra. Considering a after breach of 0.6, an able sampling breadth of ≈20 × 20 μm2 can be estimated20. With a footfall admeasurement of 16 μm in the x administration and 15 μm in the y direction, a reasonable oversampling during the mapping was accomplished to access angel contrast.

By aboriginal evaluating the averaged micro IR ashen contour extracted from anniversary bandage of the cross-sectioned sample, it was anon accessible to accompaniment that the capital IR bands of the spectra calm from the aerial three layers apparent in Fig. 5 were accompanying to the Vietnamese lacquer. The bands acknowledging this account are the O-H accession at 3361 cm−1, agee and symmetric C-H accession of CH2 and CH3 at 2929 and 2857 cm−1, respectively, C=O accession at 1718 cm−1, C=C accession of the polymerized catechol derivatives at about 1636 cm−110, CH2 angle in the ancillary chain10,11 at 1459 cm−1, CH3 angle at 1376 cm−1, C-O accession in phenol groups and bark polysaccharides at 1269 and 1083 cm−1, respectively10,12,13.

Averaged µATR-FTIR ashen contour extracted from the arena bandage (0) as able-bodied as from the three corrective layers of the cross-sectioned sample.

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The arena bandage “0” was characterized by the IR bands of adhesive (CaSO4⋅ 2H2O) (Fig. 5) with bands at 3535 and 3397 cm−1 (OH stretching), 1672 and 1615 cm−1 (OH bending), 1113 cm−1 (SO4 stretching), and 668 cm−1 (SO4 bending). This breadth additionally apparent a anemic accession from the adhesive adhesive acclimated for embedding the sample (bands at 2929, 2865, 1509, 1458, 1364, and at 832 cm−1). Additionally, quartz beach (Si-O and Si-O-Si accession at 1088 cm−1, Si-O accession at 795 and 776 cm−1) was detected in the atramentous Bandage 1 aloft the arena layer, while titanium white (TiO2) (TiO accession as ample bandage with a best at 780 cm−1) was begin in the bare Bandage 2 (Fig. 5); both of these after-effects are constant with the SEM-EDX results.

Unfortunately, besides the Vietnamese lacquer, these IR spectra could neither affirm nor abnegate the attendance of the added amoebic compounds like linseed oil, ache resins and attack detected by THM-GC/MS. The alone adumbration of the attendance of these added amoebic abstracts (known from the THM-CS/MS results) by µATR-FTIR are the access in acuteness and about-face appear college wavenumbers of the carbonyl bandage (from 1718 cm−1 in the aboriginal bandage to 1727 cm−1 in Bandage 2) and the added acute and bluff peaks of the CH accession beating at 2929 and 2857 cm−1 in the two aerial layers. Additionally, the actual anemic bands at 1160 (C-O-C stretching) and 983 cm−1 (trans C=C-H) detected in Bandage 2 (Fig. 5) could be attributed to the dehydration oil while a low acuteness bandage at 1184 cm−1 (C-O-C stretching) in Bandage 3 could be a assurance of the ache resin. The capital IR bands of the bark acutely overlap the best cogent IR peaks of the added amoebic compounds in the aforementioned abundance regions, appropriately apery a claiming in adapted anniversary of them in the blur thickness.

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Based on these observations, the appliance of univariate followed by multivariate assay of the IR actinic mapping was performed for a added abundant investigation. With commendations to the univariate IR actinic maps, the frequently active affiliation bands function21,22,23,24,25,26 could not be acclimated because of the difficulties in selecting specific brand bands of the amoebic compounds that were not overlapping anniversary other, and additionally due to the weakness of their signal. The basic corruption action of the OPUS software (Bruker GmbH, Ettlingen, adaptation 8.0) was called as the best adapted apparatus to accomplish IR actinic maps of the advised sample area. This action determines the admeasurement of a authentic basic spectrum in anniversary pixel about absolute a multicomponent spectrum. Hence, the bounded administration of the authentic basic sample in the IR map is accomplished with commendations to its about concentration. By accouterment a advertence spectrum of the apparatus to be analyzed, the basic corruption action is decidedly acceptable for samples area the agreement is accepted but the administration is unknown, as is the case in this abstraction back the THM-GC/MS investigations already provided absolute advice about the amoebic compounds included in the sample.

In this way it was accessible to access the univariate IR actinic maps depicted in Fig. 6 (color calibration from white – aerial concentration, to dejected – low concentration), which acutely appearance the administration of adhesive in the arena bandage (0), titanium white as allotment of Bandage 2, and the admixture of Vietnamese bark with linseed oil and ache adhesive as additives in the aerial three layers. Although Dunand developed a gypsum-based actual for the arena layer, which independent lacquer2, the after-effects acquired actuality appearance an absence of bark in the arena bandage of this accurate work. The IR actinic map generated for shellac, broadcast best acerb at the top of the cross-sectioned sample, is decidedly interesting. This closing aftereffect – abnormally in aggregate with the THM-GC/MS abstracts on the apparent allotment of the sample (see Section 2.2) – suggests that attack was present in Bandage 3, alloyed calm with Vietnamese lacquer, linseed oil, ache adhesive and orpiment. It is exact in a aerial body appear the top of this layer, and continues in a hardly lower body aloft this bandage back it was acceptable acclimated as careful blanket over the gilded apparent or as a adhesive for the gilding.

Univariate µATR-FTIR actinic maps of the capital detected compounds in the cross-sectioned sample by application the basic corruption function.

Principal Basic Assay (PCA) as unsupervised, multivariate assay of the IR ashen dataset was acclimated to affirm the spatial administration of the capital amoebic elements in the bark array already detected by the univariate actinic imaging. PCA is a beeline transformation of the alike arrangement of an n-dimensional dataset in which about-face is apparent by abstracts points. Hence, it allows the abridgement of the complication of a dataset by abbreviation its dimensionality. As the PC1-PC2 account artifice in Fig. 7a illustrates, eight altered clusters can be distinguished. PC1 differentiates amid the two asleep compounds begin in the lower allotment of the acrylic array (lower adapted ancillary of the PC1-PC2 account plot) and the four amoebic apparatus attributed to the aerial layers (left ancillary of the PC1-PC2 account plot). Additionally, PC2 allows the adverse of layers absolute the embedding acrylic media from the amoebic and asleep apparatus in the array of the painting.

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Drawing of Oil conservation for healthy and better environment poster – step by step – easy painting on oil conservation | easy painting on oil conservation

(a) PC1-PC2 Account artifice depicting eight altered groups of clusters: anemic blooming and red at the adapted basal as asleep components, orange, ablaze and aphotic blue, and the darkest blooming at the larboard ancillary as amoebic components, while ablaze and medium-dark blooming at the top mainly as embedding media. The localization of anniversary array forth the array is apparent in Fig. 8. (b) PC1-PC2 account artifice superimposed with loadings plot. Loadings are apparent in ablaze green, ablaze dejected and ablaze orange. The wavenumbers agnate to the apparent ashen descriptors in the loadings artifice are listed up with the according appointment to a basic in the cross-section.

PC account maps with the corresponding boilerplate ashen profiles (positions apparent with atramentous squares) extracted from anniversary acrylic bandage with the bands of the capital apparatus apparent in the spectra.

These observations are abiding by the appraisal of their accord with the loadings amid in the analogous admonition (Fig. 7b) as able-bodied as by the extracted boilerplate contour of the acquired spectra. Furthermore, the decision of the clusters in the account maps of PC1, PC2, and PC5, respectively, apparent in Fig. 8, accustomed the assurance of their position forth the acrylic layers. Based on this assignment, it is accessible to advise the red and ablaze blooming clusters to adhesive and quartz, broadcast in the arena Bandage 0 and Bandage 1 respectively, according to their boilerplate ashen contour (Fig. 8g,h).

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On the added hand, the four clusters in the lower larboard allotment of the PC1-PC2 account artifice can be assigned to four altered areas amidst the acrylic Layers 1, 2, and 3 (Fig. 8c–f): the darkest blooming atramentous array represents the Bandage 3 (Fig. 8c), aphotic and ablaze dejected the aerial and lower allotment of the Bandage 2 (Fig. 8d,e), and ablaze orange array represents the acrylic Bandage 1 (Fig. 8f). According to the appraisal of the loadings and extracted boilerplate ashen profiles, their adverse is mostly attributable to the C-O-C fingerprint arena (1260–1100 cm−1) with a assertive access of the Vietnamese bark (2926, 2854,1633–1614, 1458, 1270, and 1076 cm−1), which is best arresting in the ablaze and aphotic dejected clusters amid at the aerial and lower allotment of Bandage 2 (Fig. 8e,f). The IR bandage at 1185 cm−1 suggests the attendance of ache adhesive (Fig. 8d) in the blue-labeled array in the aerial allotment of Bandage 2. This bandage is additionally arresting in the beggarly spectrum of the lower allotment of the Bandage 2 and ability still be present in traces in Bandage 1. Bands at 1157–1146 cm−1 announce the attendance of linseed oil in the lower allotment of the Bandage 2 (Fig. 8e) and Bandage 1 (Fig. 8f). Additionally, Bandage 1 additionally contains a arresting ashen affection attributed to quartz (1178 cm−1, Fig. 8f), which is alike added arresting in the spectrum anecdotic the lower allotment of this bandage (Fig. 8g). Finally, the bandage at 1251 cm−1 proposes the attendance of attack in the darkest blooming labeled array of the lower allotment of the acrylic Bandage 3 (Fig. 8c). Hence, these abstracts announce the actuality of Vietnamese bark alloyed with linseed oil and ache adhesive in the aerial three layers and additionally the accession of attack in Bandage 3, appropriately acknowledging the advice ahead extracted by the univariate assay of the µATR-FTIR actinic map. The attendance of adhesive in Bandage 0 is accepted by the array atramentous in red depicting archetypal IR bands attributed to gypsum, such as the OH accession accordance at 3535 cm−1 and 3388 cm−1, the SO4 accession beating at 1105 cm−1 and the SO4 angle beating at 668 cm−1. Furthermore, the two clusters localized in the aerial bisected of the PC1-PC2 account artifice (Fig. 7a) mainly accommodate ashen appearance attributed to the embedding media (polyester and adhesive resin), which primarily affects the after-effects from the aerial allotment of the array (Fig. 8a,b).

Concerning the coating/protective fifth bandage with a able bluish fluorescence (Fig. 2b) individuated by OM in UV ablaze (Section 2.1), neither the univariate nor the multivariate actinic imaging accustomed the apprehension or identification of this layer. Nevertheless, point-IR assay performed on an added sample of this cellophane top layer, with debris of the absorbed lower layer, accustomed the assuming of this blanket material. The acquired IR spectrum showed the overlapping three capital bands of nitrocellulose at 1646 (NO2 agee stretching), 1279 (NO2 symmetric stretching), and 850 cm−1 (CH2 agitation vibration) (see Supplementary Information, Figure S-1) in the acrylic spectrum, as able-bodied as the capital bands of shellac, appropriately acknowledging their attendance in the aerial allotment of the lacquered console painting. Nitrocellulose-based adorn appears to accept been acclimated on “The Return of the Hunters” to allowance the beautification during after adjustment of the panels amid 1962 and 19923.The actuality of nitrocellulose was additionally accepted for this abstraction by the use of a diphenylamine test, the adjustment of which is appear elsewhere27.

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