Breaking down banners: analytical approaches to determining the materials of painted banners
© The Author(s) 2016
Received: 21 December 2015
Accepted: 26 June 2016
Published: 8 August 2016
This paper investigates a range of analytical techniques to yield information about the materials and processes used in making painted banners. A textile conservator, technical art historian and paintings conservator, and materials scientist have joined forces to develop a greater understanding of the potential of analytical findings in the identification of materials.
Visual examination using low level magnification and microscopy proved to be a crucial starting point and for identification of areas for further analysis. High magnification microscopy of cross sections was invaluable to gather information regarding the build-up of the layers, their interaction and condition. Scanning electron microscopy (SEM) of ion-milled samples showed that different areas of the banner had been prepared in different ways. SEM-EDX (scanning electron microscopy energy-dispersive X-ray spectroscopy) confirmed the presence of the main elements of pigments. Raman enabled identification of specific pigments. Raman also provided confirmation of specific materials (such as the paint filler). Fourier transform infrared spectroscopy with attenuated total reflectance (FTIR-ATR) enabled the identification of oil and resin, confirmation of pigments and fibres. Thin layers made sampling and identification challenging. Presence of materials such as silk and lead white dominated some analysis making interpretation of other materials more difficult.
Sample preparation had a significant bearing on the effectiveness of the analysis. Ion-milling provided high quality surface on the cross section samples that enabled material interfaces to be clearly seen. The challenges of finding effective wavelengths for analysis of samples using Raman were clearly evident in this study. Microscopy showed fibres blends, easily missed using FTIR, whereas FTIR was particularly effective in the identification of man-made fibres. While portable instrumentation may be useful, for in-depth understanding of the heterogeneous layered materials sample taking still remains crucial. Commercial makers used many typical grounds and pigments but these were used sparingly, in thin layers, in order to produce a flexible object and also perhaps to reduce costs. The textile was however of high quality, in this case silk. Unexpectedly, the preparation layers do not appear to be consistent across the banner; the reasons for this need further investigation.
KeywordsPainted textiles Banners Conservation Analytical techniques Degradation Microscopy Spectroscopy
Banners are iconic objects. Many images have been captured showing them billowing in the wind embellished with bold designs as they were carried on procession. They were and are still widely used by political groups, trade unions, friendly societies, churches and women’s organisations . Early banners were painted by sign writers, coach painters or decorators but during the nineteenth century many were made by commercial companies such as George Tutill and Co. and Toye, Kenning and Spencer. Many different materials (e.g. silk, cotton, linen and man-made fibres) and paints (e.g. oil, watercolour, acrylic) have been used. Banners are painted on one side or on two sides of the same fabric or consist of two painted fabrics sewn together. In most cases the paint does not cover the entire surface of the fabric. As they were designed to be carried they have poles sleeves or hanging tabs along the top and sometimes also on side edges. Despite the uncovering of hundreds of painted banners in many collections in the UK, we still know very little about their materials, construction and factors affecting their degradation. In recent years, textile conservators have been working more closely with scientists to develop a better understanding of the materials that comprise banners and painted textiles in general [2, 3].
In this study, the analysis of a typical marching banner is carried out to determine the value of techniques commonly used in the analyses of both paintings and textiles, and their appropriateness for the identification of materials and degradation processes, to inform conservation and collection care as well as add to the historical understanding of these objects. Knowledge gained through the different analytical stages shows the potential of each technique and the difficulties that these techniques present. A 1950s banner from the manufacturer George Tutill & Co. is used as a case study for this purpose.
The identification of materials is done using widely utilised instrumentation such as microscopy, scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), Raman etc. In addition to identifying the materials, the challenges associated with these types of objects in terms of sample preparation and subsequent analysis is discussed. Lastly the use of specialised preparation techniques such as ion-milling are reported. The results will enable conservators to see the value of materials analysis to their work. This study of a hierarchy of analytical techniques shows the role of different techniques in developing our understanding of painted textiles.
Object and reconstructions
Sample position, area detail and sample type
Sampling positions (detailed Fig. 1a)
Above second button from top on ladies jacket
Cross sections and loose threads
Paint from edge where silk is split, above ladies shoulder
Cross section and paint scraping
Silver painted area in line with lady’s bottom button
Edge of scroll, wine paint above the full stop after No. 77
Cross sections and paint scraping
Reconstructions of silk fabric coated with a preparatory layer of latex rubber or rabbit skin glue followed by a paint layer of zinc white pigment mixed with linseed oil were made in order to determine if the analytical methods used to identify the materials were successfully detecting the materials in each layer. These were created based on a 1861 patent (George Tutill & Co.) for the preparation of painted banners, as published by Labreuche  who reported on the nineteenth century use of latex rubber in the preparation of painted canvases, and on a discussion with banner makers George Tutill Flags (April 2014).
Low magnification microscopy was carried out using a Zeiss stereo-microscope (Stemi SV 11). Loose fibre samples were studied using a Zeiss Axiolab Pol (polarising microscope).
Embedded cross sections were prepared from samples by mounting them in clear light curing resin (Technovit 2000LC, Kulzar). The resin blocks were prepared in silicone moulds and were cured in a UV curing unit (Technology Cu, Heraeus) for 30 min. The final polish was carried out using 12,000-mesh Micro-Mesh® polishing paper. Although the polishing removed the majority of the resin some remained on the sample due to the non-conformal nature of painted cross-section. In addition it was difficult to polish painted textile to the same level of traditional oil paint cross-section because of the presence of the textile fibres tended to be abraded unevenly. Embedded cross sections were examined under visible and ultraviolet illumination using an Olympus BX41 microscope and Olympus Stream Start 1.8 image analysis software.
Scanning electron microscopy with energy-dispersive X-ray spectroscopy
Samples of the banner were viewed using an energy-dispersive X-ray (EDX) micro-analysis in conjunction with scanning electron microscopy (SEM–EDX), Camscan DX 4800 scanning electron microscopy and secondary electron, backscatter electron and absorbed current detectors (SEM-BSD, SE and AEI) and a Carl Zeiss EVO MA15 variable pressure W SEM with Oxford Instruments AZtecEnergy EDX system with 80 mm X-Max SDD detector-secondary and backscattered imaging, EDX elemental mapping and linescans plus CZ STEM detector. The analysis depth is commonly around 1 to 2 µm and the lateral dimensions tend to be about 1 µm. The quantitative results progressively improve as the element becomes heavier. To achieve very smooth surfaces, some samples were ion-milled using a Hitachi IM4000Plus ion polisher. The following instrumental conditions were used: flat milling with sample rotation and periodic beam irradiation interruption, beam-on for 1 rotation (25 rpm, means 2.4 s), beam-off for 27.6 s (30 s period) total processing time 99 min (beam-on total 475 s), beam energy 4 keV, beam current ~135 µA, and irradiation angle 60° from vertical and zero excentricity.
Fourier transform infrared spectroscopy with attenuated total reflectance
Fourier transform infrared spectroscopy with attenuated total reflection (FTIR-ATR) was carried out using Perkin Elmer Spectrum One FTIR Spectrometer with Spectrum software version 5.0.1 and fitted with a Universal ATR Sampling Accessory. The ATR crystal used was a diamond/thallium-bromoiodide (C/KRS-5) with a penetration depth up to 2 µm ATR-FTIR is primarily a surface technique and the exposed diameter of the crystal was 1.33 mm resulting in a sample area of around 1.39 mm2. 32 scan accumulations were used at a resolution of 4 cm−1.
Micro Raman analysis was carried out on two instruments which allowed the use of a total of four excitation wavelengths. The first instrument was a Renishaw inVia Raman Microscope, with Wire 3.4 software. It was calibrated using silica at 520 nm. Two excitation wavelengths were used for analysis; a gas laser source at 488 nm wavelength with a possible maximum power of 10 mW and a diode laser of 785 nm wavelength with a maximum power at sample of 200 mW. Full power was never used for either wavelength and was 5 % or less of full power. The 488 nm excitation wavelength grating had 2400 lines mm−1 and the 785 nm excitation wavelength has 1200 lines mm−1 both had a 1040 × 256 CCD detector. Further work was done on a LabRAM HR system, manufactured by Horiba Jobin–Yvon equipped with a Ventus 532 laser system 100 mW and a Helium Cadmium IK3201R-F, 20 mW, 325 nm, using a 1024 × 128 CCD detection system. Analysis was carried out on this instrument using excitation wavelengths of 532 nm and 325 nm, with gratings of 600 and 1200 lines mm−1 respectively. On both instruments the samples were focused using 20× and 50× objectives. The spectral resolution ranged from 1 to 4 cm−1 depending on the wavelength employed and the measurements were performed with a slit opening of 65 µm.
Visual inspection and low level microscopy
The condition of the textile, paint and paint-textile interfaces including presence of soiling, creasing, splits and abrasion were documented based on visual and low-level microscopy. The differences in flexibilities between the painted and unpainted areas were evident. Paint deformation resulting from previous storage around the narrow banner pole and areas of paint loss associated with flexing and creasing are evident (Fig. 2c, d). Some of these distortions may be the result of different flexibilities of the materials but also different responses to environmental conditions between the painted and unpainted areas. This damage is typical for banners .
Under low level magnification micro-cracking of the paint surface and paint losses (Fig. 2c, d) were visible, particularly on the areas with several layers of paint.
SEM and EDX
All the FTIR analysis was done using the external ATR arm and thus is considered macro (bulk) analysis. A large range of materials was identified.
The banner exhibited areas of an opalescent bloom previously reported to be present on marching banners and which could be attributed to the formation of metal soaps [17, 18]. The simultaneous presence of free fatty acids in the binders and metals from pigments make the formation of soaps predictable . However micro-pitting of the paint surface or mould are also known to cause bloom. The spectrum of a sample from P4 showed two strong sharp bands between 1500 and 1600 cm−1 one at around 1586 and another at 1538 cm−1 as a result of COO- asymmetric stretching associated with calcium soaps [20, 21]. The CO 3 −2 of CaCO3 creates a broad band at around 1400 cm−1 which masked the symmetric bands of the calcium soaps. However by performing first derivative calculations, the overlapping peaks could be seen at around 1472, 1433 and 1420 cm−1 which are all absorbance bands present in calcium soaps. The formation of the soaps is also confirmed by the reduced presence of the C=O ester and acid stretching at 1700–1750 cm−1 associated with the linseed oil components. Despite the presence of lead white detected on most of the samples from the banner the formation of lead soaps, on the samples analysed, was not detected as the doublets associated with lead soaps occur at lower frequencies 1540–1500 cm−1  and these were not seen on the spectrum. However, this may be due to the use of macro FTIR and it may be that the use of micro FTIR may have found these soaps to be present. Therefore it cannot be deduced from these results that they were not present.
Fourier transform infrared spectroscopy microscopy was not carried out here. This technique is able to achieve high spatial resolution and gains in sensitivity in detecting trace materials and it may have yielded information on the specific location of materials in the unembedded samples. However, the problems associated with bands from resin interference in embedded samples often prevents identification of oils resins etc. as the absorbance bands associated with these appear in the same parts of the spectrum. Much research is being done to prepare successful cross sections in materials which have less detrimental effects on the analysis [24, 25].
Problems with intense fluorescence signals from organic materials and dyed fabrics have been documented [28, 29]. These signals often mask the signals for the lesser reacting molecules. The use of confocal Raman microscopy has been reported as a way to prevent this  and Lorenzetti et al.  reported on its usefulness to determine the dyes on historic dyed cotton yarns by using a confocal condition 2–3 µm lower than the fibre surface. However Macdonald et al.  reported that the results often included output from both above and below the point of focus and so these contributed to the Raman response albeit to varying degrees. Thus the use of confocal microscopy may not be ideal as it is not always certain which area in the sample yields the results. When using Raman to analyse samples from painted textiles the presence of the textile such as silk, as well as the typical organic oils and resins associated with pigments, mean that fluorescence signals will be strong from such samples so care has to be taken when processing these results.
In summary a total of four different wavelengths were used in the analysis, ranging from 325 nm in the ultra-violet range, 488 and 523 nm in the visible range and 785 nm in the infrared region. The analysis of cross sections, either loose or embedded, was most successful using an excitation wavelength of 785 nm. Relatively strong signals were obtained using short scan times typically of around 10 s. Using the excitation wavelength 325 nm reduced fluorescence but failed to detect pigments, excepting lead white, or silk with any degree of certainty. Similarly Burrafato et al.  compared the use of three excitation wavelengths 531.5, 632.8 and 780 nm for the identification of pigments both dry and in egg tempera, casein tempera, oil and fresco. They reported that the presence of other materials often made detection difficult or impossible e.g. cinnabar in oil could only be detected using 780 nm. The use of Fourier Transform (FT) Raman at 1064 nm has been reported to be useful for the determination of organic materials such as dyes as it does not suffer from fluorescence interference. The signal from the sample is weakened at this wavelength  however the use of a sensitive single element such as indium gallium arsenide or liquid nitrogen-cooled germanium plus an interferometer converting the Raman signal greatly improves the output. Perhaps this wavelength’s use, due to reduced fluorescence, would have helped in identification of some materials here.
From the samples analysed a range of pigments, lead white, calcium carbonate and red lead were identified. EDX alone detected the presence of aluminium which was a component of the silver coloured paint used. The presence of oil was detected as a component within the pigments with no indication that the recently developed acrylics had been used. Shellac was most probably used to create a glazed appearance on the banner and also used to coat the wooden support pole.
Material identified, position on banner and technique used
Raman; SEM-EDX; FTIR-ATR
Light microscopy and FTIR-ATR
Light microscopy and FTIR-ATR
Light microscopy and FTIR-ATR
Visual examination using low level magnification and microscopy proved to be a crucial starting point to understand the nature of the materials being studied and to identify areas for further analysis. It is clear that important information can be gleaned from visual observation and low level microscopy.
A cross section through all layers was invaluable to gather significant information regarding the build-up of the layers, their interaction and condition. Sampling paint alone was problematic as the paint layers were very thin and crumbled easily and it proved difficult to sample the layer closest to the silk. Additionally the flexibility of the silk also created more movement than sampling from a taut canvas. Sample preparation had a significant bearing on the effectiveness of the analysis. Ion-milling provided high quality samples for SEM that enabled the material interfaces to be clearly seen. Of particular interest was the presence of an organic preparatory layer on some areas of the silk which may explain the darkening on the silk around the edges of the paint. This was not visible on samples which were prepared by polishing with cloths.
Scanning electron microscopy energy-dispersive X-ray spectroscopy confirmed the presence of main elements whereas Raman enables identification of specific compounds. The challenges of finding effective wavelengths for analysis of samples using Raman were clearly evident in this study. Previous work using Raman by Macdonald et al.  concentrated on identification of paint pigments used in painted banners as the authors stated that this would assist conservators to understand degradation as well as helping with dating and attributions. This is certainly true but to determine where degradation has occurred other materials (such as base and preparatory layers, grounds and varnishes) used in painted banners must also be identified. Raman analysis also provided confirmation of specific materials (such as paint fillers) which is useful in building a better understanding of the banners.
Fourier transform infrared spectroscopy with attenuated total reflectance enabled the identification of oil associated with the pigment, shellac used for glazing and coating the support pole, further confirmation of pigments and man-made fibres. The use of microscopy (longitudinal and cross section) was very effective and clearly showed mixed fibres. FTIR was particularly valuable in identifying manmade fibres as they can be difficult to determine using microscopy alone. This highlights the value of comparative techniques and is an important consideration, as fibre blends are not uncommon in banners.
The use of other non-invasive techniques will be important to be able to study a wide range of banners. Portable instrumentation, although not reported here, is obviously of great value in the study of painted banners as these will give a preliminary result which for example may identify a material or show surface cracking. However, portable FTIR (for example ATR and diffuse reflectance infrared Fourier transform spectroscopy-DRIFTS) is not always the best option when dealing with uneven, partially degraded, multi-layered materials as the depth of penetration could lead to erroneous results due to the complexity of spectra produced. Portable Raman may not be suitable due to the levels of fluorescence caused by the organic materials. However their application using different wavelength detectors would need to be further investigated to determine its usefulness to fully understand painted textile materials and construction.
The focus of this investigation was to systematically identify the types of materials used by the banner maker which is crucial to not only understanding the materials used in its making but also to inform conservation. This included not only the textile and paint but also other components such as the coating on the wooden banner pole. Understanding the characteristics of all materials is considered important as some materials present may contribute to accelerated degradation of others.
The presence of the silk textile resulted in more complex experimental sample preparation and also problems resulting in interference signals from the textile during some instrumental analysis. These range from the problems encountered in FTIR with dominant signals in macro analysis which results in materials not being identified to the problems of protein stains where the presence of silk can obscure other proteins which are only present tiny quantities. The challenges of finding effective wavelengths for analysis of samples using Raman were clearly evident in this study.
Sampling provided very valuable information about the banner’s construction and materials; this is a well-recognised technique used in paintings analysis for conservation. The full cross section including the textile, albeit destructive, in particular yielded not only information about the banner’s materials but also their interfaces which is crucial in understanding the composition and also to better understand its manufacture, and deterioration. This is essential to inform conservation. However taking full cross section samples would not be possible on many banners, unless there was significant damage through the painted areas, and where the paint does not extend to the edge of the object. Taking any sample from a painted banner is challenging due to the fact that the textile is not rigid and also that the paint layers are extremely thin (often around 10 µm). This means that it is difficult to achieve a cross-section of the paint layers alone as the thinness causes the paint to crumble. This is not necessarily the case with samples from paintings where the layers are usually much thicker.
Sampling from a variety of areas is important as materials and preparatory layers may vary within a banner as reported here and although portable instrumentation may be useful for in-depth understanding of the heterogeneous layered materials sample taking still remains crucial. While instrument manufacturers increasingly develop instruments that are ‘easy to use’, ultimately the value of analysis should be in rigorous interpretation and knowledge of the limitations of the instrumentation, something that can only be achieved by an understanding of the scientific principles behind the analysis. Conservation scientists perform a valuable role for conservators and curators who often only wish to identify or confirm the presence of a material, leading to the publication of many extremely enlightening and informative technical papers, but the results do not always speak for themselves. More in-depth examination and interpretation is required in order to fully understand interactions at interfaces and surfaces which will in turn help the conservator to understand and more effectively preserve these socially significant cultural objects.
MJS and KT prepared the samples, performed analyses, interpreted the results and wrote the paper. EH carried out the interpretation of the light microscopy samples. All authors read and approved the final manuscript.
Margaret Smith was funded by the Getty Foundation through the Research Network for Textile Conservation, Dress and Textile History and Technical Art History and AHRC Grant AH/M00886X/1. The authors wish to thank Frances Lennard for useful discussion during to preparation of this article. Also the authors which to thank the following people for their help in carrying out the analysis, Dr. Mark Richter, University of Glasgow; Dr. Lore Troalen, National Museum Scotland; Prof Anne Neville and Dr. Chun Wang, Institute of Functional Surfaces, University of Leeds and Mike Dixon and Dr. Thomas Schmidt, Hitachi Instruments.
The authors declare that they have no competing interests.
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