Technical Study

Analysis of a Housewife

Christina Ritschel

Technical Study May 24, 2005

Christina Ritschel, May 14, 2005

Table of Contents I. Abstract 3 II. Introduction 3 III. Experimental Procedures 5 IIIa Experimental Design 7

Analysis of the fiber and dyes 7 Analysis of the pincushion filling 9 Analysis of the metal thread and filaments 9 Analysis of the glass beads 10 Analysis of the ornamental mirrors 10

IV. Results 12

Fibers and dyes 12 Pincushion filling 13 Metal threads and filaments 15 Glass beads 17 Ornamental mirrors 18

V. Discussion. 19

Fibers and dyes 19 Pincushion filling 21 Metal thread and filaments 22 Glass beads 23 Ornamental mirrors 24

VI. Conclusion 25

Fibers and dyes 25 Pincushion filling 25 Metal threads and filaments 25 Glass beads 25 Ornamental mirrors 26

VII. References 26 VIIa. Working bibliography 27 VIII. Acknowledgements 28


I. Abstract A number of different analytical techniques were employed in order to study the different decorative components of a nineteenth-century housewife or sewing bag. Four areas examined were 1) fibers and dyes, 2) metal thread and filaments, 3) ornamental mirrors, and 4) glass beads. In order to identify the materials used and the manufacturing techniques the methods of optical microscopy, X-radiography (X-ray), X-ray fluorescence (XRF), Fourier Transform Infrared Spectroscopy (FTIR), Scanning electron microscopy energy (SEM-EDS), Gas chromatography (GC), High performance liquid chromatography (HPLC), and Raman spectroscopy (Raman) were employed. II. Introduction

The object of interest is a housewife or a sewing bag, which can be rolled upon itself. It is dated around 1800-1860 and is probably of North American origin although no research of origin has been carried out. The term housewife has developed from the old English word hussif. Another term also used is huswif. These sewing bags were used by women in the eighteenth and nineteenth century. When not in use they were rolled up and stored in the detachable pockets worn between the skirt and the petticoats (Weissman and Lavitt, 1987). There are several other housewives in the collection of Winterthur. The thirteen examples surveyed in Needlework Study are all believed to have belonged to women and used for needlework (see figure 1). Examples elsewhere are known to have belonged to soldiers. These are larger but were also used as sewing bags and called housewives as well. During the Civil War soldiers carried their housewife with sewing implements or other things (Smithsonian National Museum of American History, 2004). The exhibition, The Price of Freedom: Americans at War, shown at the Smithsonian National Museum,

included a housewife (see figure 2). The term is even listed on a web site for war slang from WWI and WWII (Wakefiels Family History Sharing, 2004).

The housewife examined during this technical study is very decorative and quite different from other housewives in the Winterthur collection (see figure 3). None of them have any inorganic components decorating the surface and they appear much more utilitarian. The housewife examined for this report is ornately decorated and might have been intended for

open display since the three-dimensional nature of the surface elements do not facilitate rolling, which in return would hide the decorations. There are signs of use, however, in form of pinholes on the pincushion and fold lines on the green back panel. The front is decorated with metal threads, metal filaments, glass beads, mirrors, and dyed pieces of fabric. It is the purpose of this technical study to carry out an extensive technical analysis on each of the decorative elements in order to distinguish manufacturing techniques and material composition. That will include analyzing the textile fibers, the dyes, the metallic components, the glass beads, and the mirrors. Analyzing each of these components may narrow the date and region

Figure 2 shows a soldier’s housewife from the Smithsonian collection currently on display during the exhibition The Price of Freedom: Americans at War.

Figure 1 shows examples of other housewives in the Winterthur collection. These are on view in Needlework study.

Figure 3 shows views of the housewife from the front (left) and from the back (right). The front is decorated with a range of inorganic elements and different colored pieces of silk. The back is covered with green silk. The green silk covering the back of the pincushion has a darker green hue than that of the panel.


for the object in addition to expanding our knowledge about its historical context.

The housewife has a pincushion at one end and a 15¼ inch long panel of layered fabric on the other side. The front of the housewife is of cream colored fabric and the reverse is of green colored fabric. Both the cream and green colored fabrics have the appearance of silk. On the back the green fabric on the portion of the pincushion has a darker appearance than the green fabric on the rest of the panel (see figure 3, right). There is strong evidence that the housewife was used regularly. There are many pinholes on the surface of the pincushion (see figure 4) and the green silk on the back have been stretched as a result of rolling the housewife for storage leaving fold

lines. A fibrous material resembling paper can be seen through some of the pinholes. The edge of the housewife is trimmed with metal threads and flat metal strips (see figure 5). Around the panels the metal threads and the flat metal strips have been worked together into a lace pattern but around the pincushion the decoration consists of flat metal filaments only. These have been woven between yellow threads to form a narrow ribbon. At each corner of the pincushion the metal ribbon has been arranged in a bow. The panel is divided into five sections. The four sections closest to the pincushion have pocket openings for storage of small sewing items.

The surfaces of each of the five sections are decorated with a variety of materials. The opening across the panel of all the sections is decorated with the same woven metallic band as the edge of the pincushion. The section closest to the pincushion is decorated with an anchor of yellow metal foil surrounded by curly metal wire (see figure 6). It is possible that the anchor is

significant to the maker but more research is needed to verify that. The second section has a small, oval mirror in the center surrounded by a flat metal band arranged as a row of metal wire shaped as figure-eights (see figure 7). The mirror is made of glass coated with a reflective material on the back side. Blue, orange, and white glass beads of either circular or cylindrical shape are sewn onto the surface in a symmetrical pattern around the mirror. The same curly metal wire used around the metal anchor is sewn onto the surface of this section

forming a wavy design around and between the beads and the mirror. The third section has a similar design but with a larger semi-circular mirror in the center surrounded by the same row of metal figure-eight patterns (see figure 8). Glass beads are also sewn to the surface in a symmetrical design. Blue beads are used as on the second section and reddish brown and yellow beads

are added. The space around and between the beads and the mirror is also ornamented with the curly metal wire. Four oval pieces of dyes fabric is inserted within areas created by the curly wire. There are two green pieces on the side towards the pincushion and two blue pieces on the area towards the end of the panel. The fourth section has a trapezoid shaped mirror in the center surrounded by the figure-eight shaped metal band (see figure 9). Blue, orange, yellow, and white glass beads are sewn symmetrically around the mirror and surrounded by the curly metal wire. Dark green pieces of fabric are inserted within the oval areas created by the curly wire, giving the impression of leaves of a flower. The fifth and last section is the rounded end of the panel. It is decorated with a stylized flower with the curly wire as stem

Figure 4 shows a detail of the pincushion with the many pinholes.

Figure 5 shows a detailed image of the different metal threads and filaments employed on the surface.

Figure 6 shows a detail of the anchor decorating the pocket closest to the pincushion.

Figure 7 shows a detail of the second pocket decorated with an oval mirror.

Figure 8 shows a detail of the third pocket decorated with a semi-circular shaped mirror. The mirror degradation is clearly visible.


and pieces of fabric in dark green and blue as flowers (see figure 10). Orange and reddish brown glass beads create two smaller flowers on the lower portion of the section. Green colored glass beads are sewn around some of the fabric flowers. The tip of the panel is pierced and some of the cream colored and green fabric is missing (see figure 11). It appears as if the housewife might have been pulled from that end, which over time created the tear.

Through the tear it is possible to see that the end is lined with paper. Each of the pockets is also lined with paper. Each mirror is visible through an opening cut in the in the cream colored silk. The mirrors were placed there and the underside was lined with paper. Fabric of the same green color as the back of the housewife was attached underneath the paper to support the mirror. On the section with the oval shaped mirror the green fabric lining is only big enough to cover the underside of the mirror exposing the lining paper on the rest of the underside. The section with the metal anchor has no fabric lining.

There is a long history of analyzing textiles, in particular dyes. Various studies using different methods have been carried out (Tímár-Balázsy, 2000). X-ray fluorescence is used to identifying dye mordants (Green and Daniels, 1990), and inorganic mineral dyes (Gardiner, Carlson, Eaton, and Duffy, 2000). Another non-destructive method commonly described in the literature is fiber optic reflected spectroscopy (FORS) (Saltzman, 1986). Raman spectroscopy is a comparatively new method for dye analysis (Witnall, Clark, Cooksey, and Daniels, 1992). Scanning electron microscopy has been used for morphology studies and when coupled with energy dispersive X-ray spectroscopy for detecting dye mordants (Koestler, Sheryll, and Indictor, 1985). Fourier transform infrared spectroscopy has been successful in identifying dyes from just a single fiber (Gillard, Hardman, Thomas, and Watkinson, 1994).

Finally, extensive work has been done with chromatographic methods (Schweppe, 1989, and Quye and Wouters, 1992). The recent book from Hofenk de Graaff (2004) is an amazing source of information on natural dyes analyzed by high performance liquid chromatography. Studies of non-textile elements similar to the ones present on the surface of the housewife are multiple and they are well documented. Several studies of metal threads and filaments are available (Darrah, 1987). The deterioration and conservation of mirrors is discussed in the literature (Davison, 2003) but technical analysis of historic mirrors is sparse (Hadsund, 1993). Different techniques for analyzing historic glass have also been introduced (Davison, 2003). Since 1975 the use of Raman spectroscopy for glass analysis is increasing (Carabatos-Nédelec, 2001 and Casadio, 2004)

None of these scholars have analyzed examples of similar sewing bags but the decorative elements present on the object are commonly used on other textile objects that have already been studied. So analyzing the housewife might not yield any new analytical information but it will add to the pool of existing experimental data and will assist future research. However, the conclusion from an extensive technical analysis of the housewife give a better understanding of the manufacture and effort laid in such small domestic textile objects.

III. Experimental Procedures

A variety of different analytical techniques were used to analyze the varied materials used in making the housewife. These techniques include Optical microscopy, X-radiography (X-ray), X-ray fluorescence (XRF), Fourier Transform Infrared Spectroscopy (FTIR), Scanning electron microscopy energy (SEM-EDS), Gas chromatography (GC), High performance liquid chromatography (HPLC), and Raman spectroscopy (Raman).

Figure 9 shows a detail of the fourth section of the front decorated with a trapezoid shaped mirror. This mirror is the most degraded.

Figure 10 shows a detail of the fifth section of the front decorated with a stylized flower.

Figure 11 shows a detail of the torn tip. It might have had a similar strap for closing as seen on figure 2.


Optical microscopy is used for fiber identification and to obtain visual information of the sample before it is used in SEM-EDS. A Nikon Type 120 binocular microscope was used.

X-radiography is used to reveal details of the composition and structure of an object when it is exposed to high energy electromagnetic radiation. The images were traditionally obtained on photographic film, which had to be developed. Today new equipment has been developed and it is now possible to collect the x-ray image on the computer within short time after exposure. The equipment used was Pantak Seifert X-ray systems with digital control Eresco MF2. This new technique uses phosphor imaging plates to produce an x-ray image of the object. The plates are photo-stimulatable and therefore reusable, which permits the user to examine areas, which might not have been considered before due to time constraints. A diode EPIX scanner and optical reader provides interactive CRT retrieval. As with the traditional technique high density areas and materials with elements of high atomic numbers will appear lighter on the x-ray image. Increasing thickness of an object can also make the film appear lighter and must be taken into consideration.

X-ray fluorescence is a non-destructive technique used for elemental, surface analysis. X-rays are irradiated towards the object and displace some of the electrons of the inner orbitals of the material present on the surface. An electron from an outer shell jumps to fill the vacancy of the inner shell but because the inner shell is of lower energy the electron emits energy in form of x-rays as it moves to the new shell. The energy of these x-rays can be measured and the element can be characterized because the level of energy is specific for each element. The intensity of the x-rays measured is related to the concentration of the element on the object surface and with standards XRF can be used for quantitative analysis as well as qualitative. Elements with an atomic number below 19 can not be detected if the equipment does not have a helium purge. A helium purge allow for the detection of elements down to an atomic number of 11. The XRF equipment used for this technical study was an ArtTAX micro-XRF spectrometer with a metal/ceramic molybdenum tube, micro-capillary focusing tube, and an energy dispersive silicon detector. A surface area the size of 70 µm can be examined.

Fourier transform infrared spectroscopy records the vibration of molecular bonds as energy from the infrared region is absorbed by a prepared sample of the object. The wavelength where a certain vibration occurs is characteristic of the particular bond whereby different functional groups can be identified and certain classes of materials can be characterized. The obtained spectrum ranges from 4000-650cm-1 and can be compared to a library of known samples. The FTIR equipment that used for this technical study was a Thermo Nicolet Magna 560 bench with a Nic Plan microscope.

Scanning electron microscopy with energy dispersive spectroscopy. SEM is an imaging technique in which a high energy electron beam is scanned across the surface of a sample while in a vacuum chamber. The surface of the sample must be conductive and is often treated with a thin coating of carbon or in some cases gold. Some of the irradiated electrons backscatter as backscattered electrons (BSE). The number of BSEs from the surface is dependent on the elemental composition. Elements of higher atomic numbers will backscatter more electrons and appear lighter on the obtained image. Therefore the BSEs are used to analyze the surface composition of the sample. Secondary electrons are emitted by the sample itself as a result of the electron interaction and are used to obtain high-resolution image at very high magnification (10 -1,000,000x) of areas as small as 1-2 µm. When coupled with energy dispersive spectroscopy, X-rays, which are emitted from the sample when exposed to the electron beam, can be detected. The sample is placed in a vacuum chamber and elements with atomic numbers as low as 11 can be detected. SEM-EDS can produce x-ray maps of the object surface and the location of certain elements can be examined. The SEM-EDS equipment used for this technical study was an Internation Scientific Instruments model# DS-130S in conjunction with an EDAX x-ray detector and Evex model 2 microanalysis system software.

Gas chromatography is a technique that separated the different components of a sample. This occurs when the sample is passed through a column, containing a stationary phase, by a gas as the mobile phase. The higher affinity the different components of the sample have for either the stationary or the mobile phase the longer time they will spent in those phases, respectively. The mobile phase passed through the column faster and the components present in this phase will exit the column faster than components with an affinity for the stationary phase. As the components exit the column they are analyzed based on either the conductivity of the component ions as they are burnt or on the mass of the molecular ions if a mass spectrometer is coupled to the equipment. Before using this technique the sample must be prepared in order to convert the component to more volatile materials that can be detected. Different groups of materials require different ways of preparation and therefore FTIR is often


used in order to classify the material present in the sample. The GC equipment used for this technical study was a Hewlett-Packard 6890 equipped with a 5973 mass selective detector (MSD) and a 7683 automatic liquid injector.

High performance liquid chromatography is the most sensitive of the different chromatographic techniques. It is therefore often employed for dye analysis of historic textiles because the sample required is small. Like other chromatographic techniques it separates the different components of the sample but the sample can be much smaller. It uses a solid material as stationary phase and a liquid as mobile phase. The sample must be dissolved in a liquid, which is injected into the mobile phases and is under high pressure passed through the column with the stationary phase. Depending on the different affinity for either the stationary or the mobile phase the sample components exit the column at different times and can be detected with an ultraviolet/visible spectrophotometer.

Raman spectroscopy records the scattered energy from vibrations of inter-atomic bonds. Monochromatic light (514nm or 785nm) is shone onto the surface of the object to excite the molecules. Most of the excited molecules relax back to their original state and emits light of the same wavelength as that received (Rayleigh effect). 0.0001% of the molecules relax back to another level of excitement compared to the ground state and light at a slightly different wavelength is emitted (Raman scattering). The resulting spectra ranges from 4000-25cm-1 and can be compared to a library of known samples. The Raman equipment used for this technical study was a Renishaw in Via Raman microscope with a 785nm laser operating at 1% power. Raman can be performed non-destructively if the object is small enough to fit underneath the spectrometer. If the protective door can not be closed protective glasses must be worn. IIIa Experimental Design

There are five areas of interests for the technical analysis; the fibers/dyes, the pincushion filling material, the metal threads/filaments, the mirrors, and the glass beads. Below follows a description of the different areas in questions and an outline of which analytical methods were employed. Analysis of the fiber and dyes

The green fabric of the back displays a pattern of lighter striations, which follows the directions of the elements. The fabric on the back of the pincushion appears darker than the fabric on the rest of the panel. The green pieces, decorating the front of the housewife, do not display the striations and might have been dyed with a different material. It is tempting to suggest that the color difference is due to light exposure of the panel when it was wrapped around the pincushion but even the portion closest to the pincushion that would have been covered, shows a distinct color difference. The portion on the panel furthest away from the pincushion is darker, possibly because of surface dirt. The fabric on both sides of the pincushion is very stiff and might have been affected by the filling material. The dyes and other materials, which might have affected the color of the fabric, were analyzed in order to investigate those phenomena. It was possible to sample the different colored fibers, which opened the possibility for a variety of analytical techniques. For indication on the areas analyzed or locations from where samples were obtained please refer to figure 12 at the end of this section.

Visual examination with aid of stereo-binocular magnification the surface, weave structure, thread count, and fiber twist was examined. The color and color differences of certain areas were studied. Finally an idea of the fabrication techniques was obtained during the examination.

Optical microscopy was used to perform fiber identification, which in return gave an idea about the dye class used for the fibers. There are several areas where the fabric is torn or the edges are un-stabilized and it was possible to obtain a microscopic sample of the fibers to examine under the microscope. It was also used to examine samples of the pincushion filling material. A magnification between 200-400x was used and therefore only a small section of the fiber was necessary for identification.

X-ray fluorescence was employed to identify dye mordants, silk weighting agents, or inorganic mineral dyes. The housewife was placed underneath the x-ray tube. The door to the room was closed and the distance to the particular area of interest was adjusted using a camera and a remote control. An exposure of 100-300 sec. was sufficient. An x-ray batch was worn during the examination.

Scanning electron microscopy (SEM-EDS) was employed to study the surface morphology and obtain an x-ray map of the fibers. It was hoped to thereby identify the XRF findings. The equipment was


operated by Jennifer Mass. Samples for this technique were obtained from the torn area and from an un-stabilized area of the pincushion.

High performance liquid chromatography was performed to identify the dyes of three green silk samples. Traditionally a green color was obtained by dyeing first with blue and then with yellow. Often the yellow dye used is very light sensitive and historic green textiles will often appear blue today because the yellow dye has faded. It was of interest to determine if the different green colors were obtained using this traditional dye method of if a synthetic dye was used, which would help narrow the date of the housewife. The HPLC analysis for this study was performed by Richard Newman, Head of Scientific Research, MFA Boston. The equipment employed was an Agilent 1100 series capillary high performance liquid chromatograph coupled with a diode array detector (HPLC-DAD) operated between 210-700 nm, with a reference wavelength of 670 nm. An Agilent ZORBAX SB-C18 column (150mm x 0.5mm, 5 micron) was used. According to Richard Newman the samples were heated at 90ºC for 20 minutes in 1:1 (volume) 3M HCl and methanol. The extract was transferred to a vial and evaporated to dryness under vacuum. The residue was redissolved in ~30 microliters of methanol. Samples that may contain indigo were first heated in dimethylformamide (DMF), and the extract drawn off for analysis. The remaining solid sample was dried, and hydrolyzed as above for analysis.

Filling material FTIR and GC

Green front1 XRF

Pale green front1 XRF

Blue front1 XRFGreen front2

XRF and HPLC Blue front2

XRFPale pink

front1 XRF

Light green back SEM-EDS and

HPLC

Paper sample

Light green back2 XRF

Dark green back SEM-EDS, and

HPLC

Light green back1 XRF

Figure 12. The arrows indicate areas analyzed with XRF or locations sampled for analysis with destructive techniques.


Analysis of the pincushion filling X-radiography was used to study the pincushion and give an idea of the density of the filling material.

This technique has earlier been used for pincushions successfully. The housewife was placed in front of the x-ray tube and a phosphor imaging plate placed underneath. An x-ray batch was worn during exposure, which took place in a lead lined room.

Fourier transform infrared spectroscopy was used to identify the materials use as filling for the pincushion. In particular it was of interest to determine if any proteinaceous adhesive was used on the filling material. The sample of the pincushion filling material used for optical microscopy was reused for FTIR and GC (see figure 12). An extraction was obtained from the brown-orange sample by submerging it in de-ionized water for 1½ weeks. The liquid was transferred drop wise to a double well slide placed on a hotplate. Each drop was not transferred before the preceding one had evaporated. When all the water had evaporated a whitish material was present on the slide. A sample was taken from the whitish material, it was placed and flattened on a diamond disk.

Gas chromatography was performed on the same dried extraction described above. This was done with the help of Chris Petersen and Catherine Matsen. The sample was prepared for proteins, which included heating for 24 hours at 105ºC with 5.5 M HCL. The sample was then evaporated to dryness with a steam of air or N2. 50-100µL of MTBSTFA + 1%TBDMCS was added as a silylating reagent and it was heated at 60ºC for 1 hour. This solution was injected into the GC equipment and the Winterthur RTLMPREP method was used. The total run time was 40 minutes. Analysis of the metal thread and filaments

The metal lace and ribbons have corroded and lost their shine over time. The color of the flat metal strips used in the lace is at certain areas shiny, pale yellow and at other points mat, dark gray. The metal threads are made of flattened metal strips wrapped around the thread. They appear dull overall and only when viewed under magnification do they display a slight glitter. These were all analyzed in order to gain a better understanding of the manufacture techniques and the metallic composition. For indication on the areas analyzed or locations from where samples were obtained please refer to figure 13 at the end of the section.

X-radiography The x-ray obtained to study the pincushion also revealed information about the metal present on the surface of the housewife.

X-ray fluorescence was employed to identify elements present on the surface of the metal threads and filaments. This gave an idea of the original appearance of the housewife. An exposure between 100-600 sec. was sufficient. An x-ray batch was worn during the examination.

Scanning electron microscopy (SEM-EDS) This technique was employed to study the surface morphology and to obtain an x-ray map of each of the different threads and filaments. This gave a more detailed understanding of how the elements detected by XRF are arranged on the surface. The equipment was operated by Jennifer Mass.

Metal thread SEM-EDS

Figure eight metal XRF

Metal thread XRF

Curly metal wire

SEM-EDS

Metal filament SEM-EDS

Metal filament XRF

Metal foil XRF

Figure 13. The arrows indicate areas of the metal elements analyzed with XRF or locations where samples for SEM-EDS were obtained.

Curly metal filament XRF


Analysis of the glass beads The housewife is decorated with glass beads of five different colors and two different shapes; round

and cylindrical. In America the first glasswork was set up in Jamestown, Virginia around 1607-1620 followed by others in Salem, MA (1639), Pennsylvania (1682), Connecticut and New York (1732). Some written records state that glass beads were produced from the beginning to use in the trade with the Native Americans, but this has not been confirmed by archaeology (Kidd, 1979). The same author suggests that the early manufactures produced utilitarian items needed by the settlers and that glass beads were produced in abundance in Venice and probably elsewhere in Europe. By analyzing the glass composition, colorants and way of manufacture it was hoped to narrow the date and region of fabrication. None of the beads are broken and it was not possible to sample these wherefore only non-destructive techniques were employed. For indication on the areas analyzed please refer to figure 14.

Visual examination was used to determine the opacity or translucency of the color, which gave an idea of how the coloring material was applied. Air bubbles, striations, and inclusions were studied to give an understanding of the fabrication technique.

X-ray fluorescence (XRF) This technique is ideal because it is non-destructive but of the many possible network formers (boron, lead and phosphorus), modifiers (sodium, potassium, calcium and magnesium) and opacifiers (tin oxides) only potassium, calcium, tin and lead can be detected because the atomic number of the other elements is too small.

Raman spectroscopy The colored matter in the glass beads will create a Raman shift, which was used to obtain spectra of the different colored glass beads. It can also be used to identify network formers (boron, lead and phosphorus) and modifiers (sodium, potassium, calcium and magnesium).

Analysis of the ornamental mirrors

An analysis of the mirrors was of interest because the date of the object corresponds to the period when silver-backed mirrors were being developed. Traditionally tin-mercury backed mirrors were the most common type since its first production in Venice, 1507. The discovery that a mixture of silver nitrate and an aldehyde could be deposited as a thin film on glass was done in 1835 by Justus von Liebig, a German chemist (Wills, 1965). Nevertheless, it was not before around 1900 that the silver-backed mirrors became as durable as the tin-mercury mirrors, which were still made until the first part of the twentieth century (Davison, 2003).

On the housewife the glass of the mirrors is in good condition but the reflective coating underneath is in a bad condition. This is especially visible on the trapezoid shaped mirror. The coating is abraded in an

Pale yellow long bead

XRF White bead

XRF Yellow long bead XRF

Yellow round bead

XRF Green bead

Raman

Blue bead XRF Yellow long

bead Raman White bead

Raman

Red long bead XRF

Blue bead Raman

Red round bead Raman

Green bead XRF

Figure 14. The arrows indicate the glass beads analyzed with XRF or Raman.


oval pattern. The semi-circular mirror has two large abraded areas while the oval mirror only displays a thin cracked line in the reflective coating. The figure-eight metal decoration around the rim of the trapezoid shaped mirror is also in much worse condition compared with the other two areas. It would be interesting to determine if the different degree of deterioration is related to what was stored in the different pockets. This, however, is not the scope of this study. Instead the reflective material of the mirrors was analyzed in order to determine the composition and if it is the same for all three. A difference in composition could have resulted in the different states of degradation. The mirrors could not be removed because the green lining is attached to the cream colored fabric with the same thread that also fastens the woven metallic band across the surface. Therefore only non-destructive techniques were employed. For indication on the areas analyzed please refer to figure 15.

X-radiography The x-ray obtained to study the pincushion also revealed information about the mirrors present on the surface of the housewife.

X-ray fluorescence (XRF) was originally not thought to work on the mirrors because the reflective surface is present below the glass. This turned out not to be the case and it was used on all three mirrors to identify the elements present in both the glass and the reflective material. It is ideal because it is non-destructive and can be used without removing the mirrors. Some of the network formers (lead) and modifiers (potassium and calcium) of the glass are present in the spectrum and must be taken into consideration during the interpretation.

Trapezoid mirror XRF

Semi-circular mirror XRF

Oval mirror XRF

Light green back1 (back of semi-circular mirror)

XRF

Figure 15. The arrows indicate areas of the mirrors analyzed with XRF.


IV. Results The information gathered during the analysis period is summarized in the following section. Fibers and dyes The fabric used for the housewife was identified visually as silk. This was confirmed with optical microscopy. Only one fiber sample was obtained. This was from the green silk on the tip of the back panel. This was thought to be representative because the appearance for the other textile elements on the housewife is so similar. X-ray fluorescence XRF was employed on the silk to identify dye mordants, silk weighting agents, or inorganic mineral dyes. With only a few exceptions the obtained spectra showed peaks for the same elements. These are listed below in table 1. Scanning electron microscopy (SEM-EDS) SEM-EDS was employed on two silk samples to study surface morphology (see figure 16) and to verify the XRF findings. The detected elements are listed below in table 2. It is clear that there is a big difference in the elements detected compared to the XRF findings. This is discussed in detail later in the report.

Sample Elements found Acquisition timeGreen front1 K, Ca, Mn, Fe, Cu, Zn, Hg, Pb 300 secGreen front2 K, Ca, Ba, Mn, Fe, Cu, Zn, Hg, Pb 300 secPale green front1 K, Ca, Mn, Fe, Cu, Zn, Hg, Pb 300 secBlue front1 K, Ca, Ba, Mn, Fe, Cu, Zn, Hg, Pb 300 secBlue front2 Al, K, Ca, Ba, Mn, Fe, Cu, Zn, Hg, Pb 300 secPink front1 K, Ca, Ba, Mn, Fe, Cu, Zn, Hg, Pb 300 secDark green back1 K, Ca, Mn, Fe, Cu, Zn, Hg, Pb 300 secLight green back 2 K, Ca, Ba, Mn, Fe, Cu, Zn, Hg, Pb 300 sec

Table 1 shows the different elements detected with XRF of the different colored silk.

Table 2 shows the elements detected with SEM-EDS on the two green silk samples.

Figure 16 shows back scattered electron images of the two silk samples. On the left the image form the light green silk fibers and on the right the image form the dark green silk fibers.

Sample Elements foundLight green back Al, Si, P, S, K, CaDark green back Si, S, Cl, Ca


Carbo- MatchSample Major absorbance peaks (cm-1) hydrate Protein Best matches percent

Pincushion filling 1 3600-3000 O-H stretching Straw wheat 89%(brown/orange material) 3400-3200 N-H stretching Jute fiber 87%

3000-2800 C-H stretching Hibiscus 87%1660-1600 C=O stretching Jute fiber 86%1650 O-H bending Abaca fiber 86%1565-1500 C-N-H bending Logwood 85%1450-1250 C-H bending cellophane 85%1200-950 C-O stretching Brazil wood 84%

Pincushion filling 2 3600-3000 O-H stretching cellophane 82%(brown/orange material) 3400-3200 N-H stretching Straw wheat 81%

3000-2800 C-H stretching Jute fiber 78%1660-1600 C=O stretching Abaca fiber 77%1650 O-H bending Gum arabic 77%1565-1500 C-N-H bending Logwood 77%1450-1250 C-H bending Alkanet root 77%1200-950 C-O stretching Hibiscus 76%

Pincushion filling 4 3600-3000 O-H stretching Cotton fiber 98%(white paper fibers) 3400-3200 N-H stretching Ramie fiber 96%

2900 C-H stretching Ramie fiber 96%1660-1600 C=O stretching Cotton fiber 95%1650 O-H bending Flax fiber 95%1565-1500 C-N-H bending Mauritius fiber 94%1450-1250 C-H bending Flax fiber 93%1200-950 C-O stretching Hemp fiber 92%

High performance liquid chromatography Three different green silk samples were given to Richard Newman, Head of Scientific Research, MFA Boston, who preformed the HPLC analysis. The findings are listed in table 3. The possible dyes present are discussed later in the report.

Pincushion filling From the visual and optical analysis alone it was not possible to determine what the filling material of the pincushion is. The surface of the filling visible underneath the pale pink silk appears smooth and resembles paper. It was possible to obtain two samples through one of the pinholes with a pair of tweezers. From the top of the pinhole a paper like sample was removed and from further inside the pinhole a brown-orange sample was removed. Fourier transform infrared spectroscopy The two different looking materials were prepared for FTIR analysis and flattened on a diamond disc. Spectra from two different areas of the brown-orange material were obtained. The results are presented in table 4.

Sample Retention time (min) Possible component Possible dyeSample 1 (back of pincushion) Analysis not completed N/A N/A

Sample 2 (tip of panel) 14.354 Luteolin Weld, Dyer's broom, or Sawwort20.707 Indigotin Indigo or woad

Sample 3 (petal on front) N/A Not luteolin N/A

Table 3 shows the findings obtained with HPLC of three different green colored silk samples.

Table 4 shows the results obtained with FTIR on the two samples of the pincushion filling material.


Pincushion filling 1 and 2 showed stronger peaks for protein compared to pincushion filling 4. It was decided to obtain an extraction of the orange-brown material and determine if a proteinaceous adhesive was used to possibly hold the filling materials together. A sample of the dried extraction was analyzed with FTIR. The results are given below in table 5.

Gas chromatography To verify the presence of animal glue suggested by the match results obtained from the FTIR analysis of the extraction GC was performed on the same dried extraction of the brown-orange filling material. The amino acids detected are listed below in table 6. GC analysis was performed with the help of Chris Petersen.

Table 5 shows the information obtained with FTIR on the extraction of the brown-orange material from the pincushion filling.

Table 6 shows the amino acids detected with GC on the dried extraction of the brown-orange material from the filling material.

Carbo- MatchSample Major absorbance peaks (cm-1) hydrate Protein Best matches percent

Pincushion extraction 1 3600-3000 O-H stretching Tetul tree gum 76%(brown/orange material) 3400-3200 N-H stretching Valspar varnish 75%

3000-2800 C-H stretching Nikawa Gettens 74%2340 CO2 atmoshpere Wool 74%

1660-1600 C=O stretching Chardin Patin 74%1650 O-H bending Animal glue 74%1565-1500 C-N-H bending Hide glue 74%1450-1250 C-H bending Nikawa hide glue 73%1200-950 C-O stretching Rabbit skin glue 73%

Pincushion extraction 2 3600-3000 O-H stretching Chardin Patin 75%(brown/orange material) 3400-3200 N-H stretching Nikawa Gettens 74%

3000-2800 C-H stretching Valspar varnish 74%2340 CO2 atmoshpere Nikawa hide glue 73%1660-1600 C=O stretching Tetul tree gum 73%1650 O-H bending Nikawa hide glue 72%1565-1500 C-N-H bending Rabbit skin glue 72%1450-1250 C-H bending Glue Gettens 72%1200-950 C-O stretching Roman ochre 71%

Sample Significant peaks (min) ComponentPincushion filling extraction 13.51 Alanine

13.77 Glycine17.06 ?17.73 Phosphate17.95 Proline18.35 Serine18.65 4-hydroxybenzate19.43 Phenylalanine19.92 Aspartic acid20.95 Glutamic acid


Sample Elements found Acquisition timeAnchor Cu, Zn, Fe, Pb, As 600 secMetal thread Cu, Ag 100 secStraight metal filament Cu, Ag 100 secCurly metal filament Cu, Ag 100 secFigure eight metal Cu, Ag 600 sec

X-radiography Straw wheat was one of the FTIR matches for the brown-orange filling material. The color and physical structure of the sample could resemble straw and it was decided to obtain an x-ray image of the pincushion to gain a better understanding of its interior (see figure 17). This was carried out with the help of Margaret Little.

Metal threads and filaments There are five different metal components decorating the surface of the housewife. These were analyzed in order to gain better understanding of the metallic composition and possibly the manufacture techniques. X-ray fluorescence XRF was employed on the metal to identify metallic composition. The elements detected on the surface are listed below in table 7.

Figure 17 shows the two images obtained with x-ray phosphor imaging plates. Above is an overall image of the housewife and to the left a detail of the pincushion. On the left the pincushion is sitting upright supported by the storage box.

Table 7 shows the metallic elements detected on the surface of the different components analyzed with XRF.


Scanning electron microscopy (SEM-EDS) SEM-EDS was employed to obtain an image of the surface morphology and x-ray maps of the elemental distribution on the metallic surface. The elements detected are listed below in table 8. The back scattered electron images and an elemental map are shown on figure 18-20.

Table 8 shows the metallic elements detected by on the surface of the different components analyzed with SEM-EDS.

Figure 18 shows several back scattered images obtained from the metal thread with SEM-EDS. Shown on the top is a detailed image of the metal thread (left) and a detail of the striated metal surface (right). On the bottom is a detail of the silk fibers and the metal wrapped around it (left), an x-ray map of the metal (middle), and a SEM-EDS spectrum showing the detected elements (right). On the elemental map the red represents cupper, the green represents silver, and the blue represent sulfur.

Sample Elements foundMetal thread S, Cu, AgStraight metal filament (light area) S, Cl, Cu, AgStraight metal filament (dark area) Al, Si, S, Cu, AgCurly metal filament (light area) S, Cu, AgCurly metal filament (dark area) Si, S, Cl, Ca, Cu, Ag


: Glass beads Many different colored glass beads were used as decoration on the housewife. It was only possible to analyze the beads with non-destructive techniques because none was loose and could be removed. X-ray fluorescence (XRF) XRF was employed on each of the different hues represented to possibly identify the pigments used as colorants. The elements detected on the surface are listed below in table 9.

Figure 19 shows a BSE image of the straight metal filament. Striations are visible on the surface and might give indications of how the metal was flattened while worked. Both a dark and a light area were analyzed with SEM-EDS.

Figure 20 shows a BSE image of the curly metal filament. From the scale it is visible that this filament is thicker than that of the straight filament and the one wrapped around the silk fibers of the metal thread. Both a light and a dark area were analyzed with SEM-EDS.

Table 9 shows the different elements detected with XRF on the different colored glass beads.

Sample Elements found Acquisition timeBlue round bead K, Ca, Mn, Fe, Zn, Co, Ni, As, Sr, Bi 100 secYellow long bead Si, K, Ca, Fe, Pb, Sb 600 secPale yellow long bead Si, K, Ca, Mn, Fe, Cu, Pb, Sb 100 secRound yellow bead Si, K, Ca, Mn, Fe, Pb, Sb 600 secWhite round bead Sr, Ca, Mn, Fe, Zn, Pb, Sb 100 secGreen round bead Si, K, Ca, Mn, Fe, Cu, Pb 100 secRed round bead Si, K, Ca, Ba, Mn, Fe, Cu, Sr, Pb 100 secRed long bead K, Ca, Mn, Fe, Cu, Sr, Pb, Sb 100 sec


Raman spectroscopy Raman analysis was performed on the different colored glass beads in order to possibly identify the different pigments used as colorants. At the time of analysis and when writing this report the search library connected with the Raman spectroscopy was not working and the obtained spectra have not yet been matched with existing spectra in the database. The results are given below in table 10.

Ornamental mirrors It was of interest to analyze the composition of the reflective surface of the mirrors to possible narrow the date of the housewife. They could not be removed for analysis and therefore only non-destructive techniques could be used. X-ray fluorescence (XRF) XRF was employed on the glass surface of each of the thee mirrors and on the green silk on the back of the semi-circular mirror. The elements detected are listed below in table 11.

Sample Raman shift (cm-1)Blue bead 1360

1105950570400

Yellow long bead 13601210970755510339305142

Red round bead 1387273

Sample Raman shift (cm-1)White bead 1590

153013201250825350235

Green bead 19601340500

Clear microscope slide 1850159013701200560360

Table 10 shows the Raman shift detected for the different colored glass beads analyzed. All the beads and the microscope slide show a Raman shift around 1320-1387cm-1.

Table 11 shows the elements detected with XRF on the mirrors. Mercury was only detected on the backside of the semi-circular mirror.

Sample Elements found Acquisition timeOval mirror K, Ca, Mn, Fe, Cu, Zn, Rb, Sr, Pb, Sn 600 secSemi-circular mirror K, Ca, Mn, Fe, Cu, Zn, Rb, Sr, Pb, Sn 600 secTrapezoid mirror K, Ca, Mn, Fe, Cu, Rb, Sr, Pb, Sn 600 secLight green back 1(back of semi-circular mirror) Ca, Fe, Cu, Zn, Hg, Sn 300 sec


V. Discussion. Fibers and dyes

The spectra obtained when XRF was employed on the different silk surfaces displayed a strong background noise the 5-15 keV region. The high background made it difficult to recognize significant peaks. The elements detected with certainty are listed under results. Mercury is selected on all the spectra but the peak is questionable. Other elements such as manganese, copper, zinc, and lead would not be suspected as present in the silk. However, those peaks are quite significant. When analyzed with SEM-EDS none of those higher atomic elements are detected. Analysis performed by Kate Sahmel on the ethafoam and the volara used to support objects when analyzed with XRF showed larges peaks of copper for the ethafoam and peaks of zinc and barium for the volara. That might explain some of the observed peaks and others might be a result of background noise.

The dye analysis performed by Richard Newman only gave specific results for sample 2 the light green silk from the tip of the back panel. The analysis of sample 1, the dark green silk on the back of the pincushion has not yet been completed. Sample 3, the green silk piece around the trapezoid mirror, did not yield a conclusive result. Several small possibly yellow peaks were detected but Newman could only say that they were not from the yellow dye component luteolin. For sample 2 he detected the yellow dye component luteolin and the blue dye component indigotin. A mixture of blue and yellow dyes is what one would suspect from a naturally dyed green fabric. Luteolin is the major dye component for three different yellow dyes; weld, dyer’s broom, and sawwort. Weld and dyer’s broom also contain other coloring matters. For weld the second color component is apigenin and for dyer’s broom the second component is genistein. Sawwort is the only of the three that contains only luteolin. Figure 21-23 show HPLC spectra of the dyes.

Figure 21 shows an HPLC spectrum obtained from wool dyed with weld on alum mordant. The fibers were extracted with HCL.

Image form The Colorful Past (Hofenk de Graaff, 2004)


Figure 22 shows an HPLC spectrum obtained from fibers dyed with dyer’s broom. The fibers were extracted with HCL.


Newman detected no other yellow dye component than luteolin and it is possible that the yellow dye used to achieve the green color of the back panel was sawwort. The retention time around 22-23 minutes listed by Hofenk de Graaff, however, is different from the one obtained by Newman (14-14.5 min). A difference in equipment and preparation method might recount for the difference in retention time. The significant likeness or differences of the two systems have not yet been determined. The HPLC spectrum of dyer’s broom obtained by Hofenk de Graaff shows a possible peak for luteolin-5-glucoside at a retention time of 14-15 minutes. If the two systems are compatible dyer’s broom might be the dye used on the back of the panel, although its other color component Genistein was not detected by Newman. According to Hofenk de Graaff the retention time for Genistein is around 19-20 minutes and it is possible that the peak is obscured by indigotin (20-21 min) on the spectrum obtained by Newman. If the two systems are not compatible and it is not possible to use the retention times for comparison then all three dyes must be viewed as possibilities. Historic references quoted by Hofenk de Graaff states that Dyer’s broom and sawwort were used in particular to obtain green colors. Nevertheless, the presence of weld can not be ruled out. All three of the possible dyes are mordant dyes. Weld produces an orange-yellow with aluminum, a greenish-olive with iron, a bright lemon-yellow with tin, and a yellowish-green with copper. Dyer’s broom produces a pale greenish-yellow with chrome, a chocolate brown with iron, a very pale yellow with aluminum, and a yellowish green with copper. Sawwort produces a greenish-yellow with aluminum and an olive brown with iron. Historically alum (potassium aluminum sulfate) in combination with Spanish green (copper acetate) and rinse tartar is the most often used mordant (Hofenk de Graaff, 1984) for the three dyes. During the XRF analysis aluminum was only detected on Blue front2 and only as a very small peak. Copper was detected in abundance on all the areas analyzed but might be related to contamination from the foam support underneath. The signal for iron is as strong or on certain areas even stronger than copper. From that data it is difficult to determine a possible mordant. The data produced by SEM-EDS does not show these elements of higher atomic numbers. Aluminum is only detected on the light green back, which is the same light green color that was analyzed by HPLC. There is a small peak where aluminum would be detected on Dark green back but it was not selected during the analysis. In both cases the signal is weak compared to those for calcium and sulfur. Sulfur is present in the amino acid cystine found in silk but it is also possible that the sulfur detected here is from the sulfate in the alum, which might also be the case with the detected potassium. Indigotin, the other color component detected by Newman, is found in the two blue dyes indigo and woad. It is also found in various marine snails, which in antiquity were used to produce Tyrian purple exclusively used for royal and ecclesiastic members. Today it is safe to presume that only indigo or woad was used. Both dyes are vat dyes and require that the dyestuff is first reduced to the water soluble substance indoxyl before the textile is added. In the vat, water and indoxyl is deposited on the textile and as the fabric is removed from the vat the air is enough to oxidize indoxyl back to the blue colored indigotin. Because of the water fastness of indigotin both indigo and woad are very stable dyes. The both contain a second color component, indirubin. This component appears to be more prominent in indigo (Hofenk de Graaff, 2004). Figure 24-25 show HPLC spectra of the two dyes.


Figure 23 shows an HPLC spectrum obtained from wool dyed with sawwort on alum mordant. The fibers were extracted with HCL.


The retention time for indigotin seen on both spectra is around 24-25 minutes. The analysis performed by Newman showed a retention time for the compound around 20-21 minutes. Both dyes were used for dying green textiles. Indigo was introduced to Europe in the sixteenth century after an embargo from the woad producers for trade protection. Indigo later became the preferred of the two (Hofenk de Graaff, 2004).

Pincushion filling Two samples were obtained from the filling material through a pinhole on the pincushion. The appearance of the one obtained from the upper portion of the pinhole resembled paper and the best FTIR matches (98-92%) were for cotton and bast, which is typical of rag paper before 1844. The best match (89%/81%) for the brown-orange colored sample was straw wheat. Visually the sample also appeared like a piece of straw. Two different areas of the brown-orange sample and one area of the paper like sample were analyzed. The two spectra obtained from the brown-orange material both showed peaks for protein. The paper like sample showed a weaker signal for protein but it could not be ruled out. To further investigate the presence of protein in the brown-orange material and extraction was made with de-ionized water (figure 26). The dried extraction was prepared for FTIR and two spectra from different areas of the sample were obtained. Both areas showed an even stronger presence of protein and some of the library matches (76-72%) were all from animal glues.



Figure 24 shows an HPLC spectrum obtained from cotton dyed with indigo. The fibers were extracted with DMF.

Figure 25 shows an HPLC spectrum obtained from wool dyed with woad. The fibers were extracted with DMF.

Figure 26 shows a view of the brown-orange material as it is being extracted.


It is possible that if the sample is a piece of straw wheat the observed signal for protein might be related to a cereal protein. To verify this the dried extraction was prepared for GC in order to determine if hydroxyproline could be found in the sample, which would support the match for animal glue. However, no hydroxyproline was observed with GC but the various amino acid peaks were so small that they were close to insignificant and the absence or presence of hydroxyproline could not be confirmed. Gliadin is the cereal protein of wheat and according to Mills and White (2003) the amino acid composition of gliadin in order of significance is as follows; glutamic acid, proline, isoleucine, phenylalanine, serine, tyrosine, valine, arginine, cystine, alanine, threonine, histidine, methionine, aspartic acid, tryptophan, lysine. Nine of these amino acids were detected as small peaks during the GC analysis but no quantitative data was obtained. To draw a final conclusion regarding the type of protein present on the brown-orange sample more analysis must be performed.

The x-radiograph of the pincushion did not reveal much in terms of structure. No individual pieces of straw were visible within the cushion. From the x-ray image it most of all appear as a homogeneous bundle of material such as cotton. It is possible that the brown-orange piece sampled from the lower portion of the pinhole is an impurity from the cotton. The top surface of the filling has an appearance of paper and it is possible that the filling was wrapped in paper before covered with silk fabric. The addition of paper would possible hold the pins better than cotton alone.

From the x-ray image it is visible that a piece of curly wire and two round objects are included in the filling material. The curly wire is so close in appearance to those used to decorate the surface of the housewife that it most likely is the same. The round objects might be two round beads that were trapped in the filling material. For this it might be possible to conclude that the person who made the pincushion also decorated the surface of the rest of the housewife. Metal thread and filaments From the XRF analysis of the anchor it is possible to say that it is made of brass, which is a copper-zinc alloy. Yellow brass contains 34-37% zinc and has excellent corrosion resistance (Hawley, 1987). It was not possible to perform quantitative analysis with the XRF equipment used and the anchor could not be sampled for SEM-EDS. An elemental map could have been obtained with SEM-EDS and an idea of the elemental proportion could have been gained. The XRF spectrum also shows peaks for iron, lead, and arsenic. The same peak for iron was observed on the other metallic components and by consultating with Jennifer Mass it was concluded that the peak is a false positive. It is possible that the iron peak from the brass is also a false positive. Lead is sometimes seen on brasses as is tin. The x-axis on the brass spectrum given in this report has been cut off so it is not possible to see if there is a peak for tin around 25.27keV. An unmarked peak is observed in the lower region of the spectra and it is necessary to go back and determined if that peak might be from tin. The presence of arsenic is sometimes obscured by lead because their keV lines overlap. The Kβ1 line for arsenic around 11.73keV is unique to arsenic and is observed on the brass spectra indicating that arsenic is present in addition to lead. The XRF spectra obtained for the metal thread, the metal filament, the figure eight metal, and the curly metal wire show the same elemental composition of copper and silver. All four spectra have a peak that can be from iron but as mentioned above it was identified as a false positive. It was possible to sample the metal thread, the metal filament, and the curly metal wire for SEM-EDS analysis. This analysis further confirmed the absence of iron. The BSE images of the metal thread show a comparatively thin metal filament wrapped around what under a stereo binocular microscope appears as silk fibers (figure 27). The surface of the metal filament shows lines of striations parallel with the longitudinal edge of the filament. This might indicate that drawing through successively smaller holes was the method employed to flatten the metal filament. The SEM-EDS spectra and the elemental map indicate that copper is the main component of the filament and silver is present is small amounts on the surface. Sulfur was also detected and is likely from silver tarnish.

The BSE image of the metal filament shows the same striations and judging from the scale it is possible that the straight metal filament is the same as the filament used to wrap around the silk fibers. The straight metal filament also has a similar spectrum with copper as the main component and silver

Figure 27 shows a microscopic view of the metal thread. The metal filament is wrapped around what appears as undyed silk fibers.


present in smaller amounts. Two areas of the filament were analyzed; one that appeared light and one that appeared dark on the BSE image. The darker area appeared to contain more silver corrosion products like sulfur and chloride. Silicon and aluminum were also detected on the dark area possibly from surface dirt. The BSE images of the curly metal wire show that the surface is covered with what appear as corrosion products. No striation lines are visible on the surface. The scale indicates that the wire is thicker than the other two filaments. Two areas that also appeared dark and light colored in BSE were analyzed with SEM-EDS. The spectrum of the light colored area shows copper as the main component, silver in smaller amounts, and trace amounts of sulfur. The spectrum of the dark area showed silver as the main component, copper in smaller amounts, and large amounts of sulfur and chloride and some silicon. Glass beads Several elements were consistently detected with XRF and related to the glass itself. These are silicon, potassium, calcium, manganese, iron, and strontium. The silicon is from silica (sand) the main component used as a network former. Because it is the main component a stronger signal might be expected but the atomic number of silicon is too low. It might show up better with SEM-EDS but none of the beads could be removed. Potassium and calcium are used as network modifying ions, positively charged cations that neutralize the negative charge of the silicate oxygen. Potassium is also used as a network former with silicate in potash glasses. Lead is detected on many of the beads and it is also a possible network former. Strontium is sometimes detected because of its presence in calcium ores. Iron is likely to have been present in the sand used and manganese in small amounts is added to decolorize the yellow color obtained from iron (F3+). The purple of the manganese balances the yellow and results in a colorless glass (Davison, 2003). Antimony can also act as a redux reagent for iron (Jennifer Mass, personal communication). Various coloring pigments can be added to the glass and produce a final color. The XRF spectrum for the blue round bead shows that cobalt is used as a colorant. Arsenic is present in the cobalt ore as smaltite (CoAs2) and cobaltite (CoAsS) and these are often associated with the mining of nickel (Greenwood & Earnshaw, 1987). The possible pigments used to achieve the blue color are cobalt oxide or cobalt blue (Gettens and Stout, 1966). When iron is not reduced by manganese it is present as the ion Fe2+. This ion has a blue color and might contribute to the color of the bead. The presence of bismuth might be a confusion of the Lα1 peak for bismuth (10.836keV) with the Kα1 peak for arsenic (10.543keV). The peak for zinc is small and might be a false positive or maybe from the foam support underneath the housewife as discussed under Fibers and Dyes. It might also have been used in the production of nineteenth century glass and literary sources on the subject should be consulted in order to draw a better conclusion. The XRF spectrum for the yellow long bead shows the elements related to the glass itself and in addition shows a strong peak for lead and a smaller but distinct peak for antimony. Naples yellow (Pb3(SbO4)2) is the only yellow pigment that contains both lead and antimony. It is also possible that litharge (PbO) is present. Lead was also added to lower the melting point of the glass and might therefore add to the strong signal. No manganese was detected as a decolorizing agent and the yellow iron ion might add to the overall color. There is a small peak around 5.898keV where the Kα1 peak for manganese would be expected. It is possible that the element was overlooked during the examination. An excess of manganese would act as a redux reagent and change the oxidation state of iron from Fe2+ to Fe3+, which has a yellow color and would add to the overall color of the bead. The XRF spectrum of the pale yellow long bead shows the elements related to the glass itself and shows a strong peak for lead but an almost invisible signal for antimony. It is possible that a smaller amount of Naples yellow was used for a paler yellow. It is also possible that litharge (PbO) is the main colorant. Both manganese and iron are present and the Fe3+ state of iron might also add to the overall yellow color of the bead. A small peak for copper is detected but might be a false positive. The XRF spectrum for the round yellow bead is similar to that of the pale yellow long bead and it was decided to run the equipment with an acquisition time of 600sec. Again the elements related to the glass itself are detected as is a strong peak for lead but an almost invisible signal for antimony. As with the pale yellow bead it is possible that a smaller amount of Naples yellow was used for a paler yellow. It is also possible that litharge (PbO) is the main colorant and that manganese and iron result in the Fe3+ state of iron, which might add to the overall yellow color of the bead. The XRF spectrum of the white bead shows the elements related to the composition of the glass. A strong signal for antimony is detected. Calcium antimony (Ca2Sb2O7 and Ca2Sb2O6) was used in antiquity as an opacifying agent for white glass and tin was used later. Three different opacifying agents


have been used since the eighteenth century. These are calcium fluoride (CaF or CaF3), 3Pb2(AsO4)2•PbO and (Na2Ca)2Sb2O6F. Because antimony is detected (Na2Ca)2Sb2O6F is the most likely opacifying agent. It is also possible that antimony is present as a redux reagent. SEM-EDS analysis would be a good technique to use for verification. As with the pale yellow bead a peak for zinc was detected. It is small and might be a false positive or maybe from the foam support underneath the housewife as discussed under Fibers and Dyes. It might also have been used in the production of nineteenth century glass and literary sources on the subject should be consulted in order to draw a better conclusion. The XRF spectrum of the green bead shows the elements related to the glass itself and shows strong peaks for lead and copper. The copper ion Cu2+ is green and is likely that coloring state found on the bead. A mixture of iron in the two oxidation states, the blue Fe2+ and the yellow Fe3+, might also add to the shade of green. The strong signal for lead might be from its use as a flux or network former. The XRF spectrum of the red round bead shows the elements related to the glass itself and shows strong peaks for calcium, iron, and copper. In addition to its role as a network modifying ion calcium might be seen here as an opacifying agent. Copper in the form of Cu1+ has a red color and that is the likely state of the ion on this red bead. There is a small peak for barium, which might be from impurities in the silicate of from the volara used as support underneath the housewife. The XRF spectrum for the red long bead is very similar to that of the round red bead but instead of barium a small peak for antimony is detected. Copper in the form of Cu1+ is most likely the agent responsible for the red color and antimony might be present as a redux agent or an impurity. Iron oxide might also add to the red color. The Raman spectra obtained from six of the glass beads have not yet been interpreted. It is necessary to compare them to matches in the Raman library to determine if together with the XRF data any conclusions can be drawn. All the beads and the microscope slide show a Raman shift around 1320-1387cm-1. It is possible that the glass is responsible for this shift and that the other shifts are from the various coloring agents. Ornamental mirrors When XRF analysis was performed on the front surfaces of the three mirrors different elements related to the glass were detected. As described above these are potassium, calcium, manganese, iron. Strontium is sometimes detected because of its presence in calcium ores and rubidium might be present as a result of the potassium. In addition to these elements small amounts of copper and zinc were detected. These might be false positives or maybe from the foam support underneath the housewife as discussed under Fibers and Dyes. Zinc might also have been used in the production of nineteenth century glass and literary sources on the subject should be consulted in order to draw a better conclusion.

The main element of interest is the presence of tin. Mirrors with tin-mercury amalgam reflective surfaces were produced until the first part of the twentieth century. By then mirrors backed with a thin film of silver nitrate and an aldehyde were durable enough to replace the traditional way of producing mirrors. It was hoped that the date of the housewife could be narrowed by analyzing the mirrors. From analyzing the front of the mirrors it appears that the mirrors present on the housewife are of the traditional tin-mercury type. This was not certain, however, because the fluorescence of the mercury was not detected through the glass. It was therefore very exciting then the back of the semi-circular mirror was analyzed by chance during the analysis of the silk fibers. Large peaks for mercury and smaller peaks for tin were detected and it was possible to conclude that the mirrors are backed with a tin-mercury amalgam.

The x-ray image obtained of the housewife shows the whole pieces of mirror as they sit underneath the fabric front. The mirror signified as the oval-shaped mirror throughout this report is an elongated polygon and the one signified as semi-circular is closer to a rectangular shape. The mirrors are completely white compared to other components on the surface, which indicates that elements with high atomic numbers are present in the mirrors.


VI. Conclusion The findings presented in this report did not help to narrow the date range of the housewife,

1800-1860. Nevertheless, quite a bit of information was gained about the materials and the manufacturing methods. A summery of the findings is given below. Fibers and dyes

XRF analysis of the silk fibers showed peaks for copper, zinc, and barium, which might be responses from the ethafoam and volara used underneath the housewife during the analysis. This gives an idea of the depth from which the XRF equipment is able to detect when the material analyzed is organic. Other peaks detected were mercury and lead but this might just be a result of background noise.

SEM-EDS analysis of the two different green colors from the back of the housewife gave a better result for elements with a lower atomic number. Aluminum and sulfur were detected on the light green silk from the panel and might be from an alum mordant (K2SO4Al2(SO4)3 •24H2O). Signals for sulfur might also be from the cystine present in the protein of the silk.

HPLC analysis of the lighter green silk on the back panel indicated that a mixture of natural yellow and blue dyes was used to obtain the green color. The yellow dye might have been weld, Dyer’s broom, or sawwort. The blue dye might have been indigo or woad. Historically alum is the mordant most often used for the three yellow dyes, which is consistent with the SEM-EDS detection of aluminum on the light green sample. The HPLC results for the green silk pieces around the trapezoid mirror were not conclusive other than to say that luteolin was not present on the fibers.

Pincushion filling The samples removed from a pinhole on the pincushion were identified as possible paper and straw wheat. Since the paper sample was obtained from the upper portion of the pinhole it was suspected that straw was enclosed by paper and used for the cushion. However, the x-ray images show that the filling material is very homogeneous and does not appear as pieces of straw. It is possible that the sample identified as straw was an impurity within the filling material. If possible more samples should be obtained from the filling material. The FTIR analysis of the straw gave matches for animal glue but this was not verified with GC. It is possible that the cereal protein Gliadin is the cause of the protein peak on the FTIR spectra. More work with matching the spectra with the computer library should be done. Metal threads and filaments XRF analysis on the metallic components revealed that the metal anchor is made of brass. The four other elements the metal thread, the straight metal filament, the curly metal wire, and the figure eight shaped metal are all mainly of copper with silver on the surface. BSE images of the metal thread and the straight metal filament obtained during the SEM-EDS analysis show striations on the surface indicating that drawing was the technique employed when flattening the filaments. The x-ray map of the metal thread gives an idea of the elemental arrangement on the surface. Sulfur was detected on all the surfaces and might be from silver tarnish.

The straight filament and that of the metal thread wrapped around the silk are similar in width and thickness and might have been produced the same way and used for different purposes. The curly metal wire is thicker than the filaments and appears to have collected more surface dirt. A stronger signal for sulfur and chloride was obtained from the wire and it is possible that the silver on the surface is more tarnished then that on the metal threat and the filament. Glass beads The XRF findings indicated that the following colorants were used for the various glass beads.

• The blue bead is colored by cobalt and possibly iron in the form of Fe2+. • The three yellow beads, the long yellow bead, the long pale yellow bead, and the round yellow

bead are colored by Naples yellow (Pb3(SbO4)2). Litharge (PbO) and iron in the form of Fe3+ are also possible colorants. The round bead and the pale yellow bead contain smaller amounts of Naples yellow.

• (Na2Ca)2Sb2O6F is the most likely opacifying agent for the white bead because antimony is detected. It is also possible that calcium fluoride (CaF or CaF3) or 3Pb2(AsO4)2•PbO are present and SEM-EDS analysis would be necessary.


• The green bead is colored by the copper ion Cu2+ and possibly a mixture of iron in the two oxidation states, the blue Fe2+ and the yellow Fe3+.

• The round and the long red beads are colored by copper in the form of Cu1+ and possibly also iron oxides.

As of yet no interpretation of the Raman spectra obtained has been acheived. It is hoped that more work can be done on them in the future. Ornamental mirrors The reflecting film of the mirrors is a tin-mercury amalgam, which dates them before the first part of the twentieth century.

VII. References Carabatos-Nédelec, Constantin. 2001. Raman Scattering of Glass. Handbook of Raman Spectroscopy.

From the Research Laboratory to the Process line. Ian R. Lewis & Howell G.M. Edwards Eds. New York: Marcel Dekker.

Casadio Francesca. 2004. Decoration of Meissen Porcelain: Raman Microscopy as an Aid for

Authentication and Dating. Paper presented at IRUG6 conference at Palazzo Incontri, Florence. March 29 – April 1.

Darrah, Josephine A. 1987. Metal Threads and Filaments. Recent Advance in the Conservation and

Analysis of Artifacts. R.J. Black, ed. London: Summer School Press. (pp 211-221) Davison, Sandra. 2003. Conservation and Restoration of Glass. New York: Butterworth Heinemann. (pp

3-10, 76-79, 87-88, 133-135, 227-239, 332-333) Gardiner, Joy; Carlson, Janice; Eaton, Linda; and Duffy Kate. 2000. “That Fabric Seems Extremely

Bright”: Non-Destructive Characterization of Nineteenth Century Mineral Dyes via XRF Analysis. Conservation Combinations. Preprints, North American Textile Conservation Conference. Saline, MI: McNaughton & Gunn. (pp 100-115)

Gettens, Rutherford J. & Stout, George L. (1966). Peinting Materials. A Short Encyclopaedia. New York:

Dover Publications. Gillard, R.D; Hardman, S.M; Thomas, R.G; and Watkinson D.E. 1994. The Dectection of Dyes by FTIR

Microscopy. Studies in Conservation, 39. London: James & James. (pp 187-192) Green, Lorna R and Daniels, Vincent D. 1990. Identification of Mordants Using Analytical Techniques.

Dyes in History and Archaeology 9. Papers presented at the 9th annual meeting, York. York: Textile Research Associates. (pp 10-14)

Greenwood, N.N. & Earnshaw, A. (1989). Chemistry of the Elements. New York: Pergamon Press. Hadsund, Per. 1993. The Tin-Mercury Mirror: Its Manufacturing Techniques and Deterioration Processes.

Studies in Conservation, 38. London: James & James. (pp 1-16) Hawley, Gesser G. (1987). Hawley’s Condensed Chemical Dictionary. Revised by N. Irving Sax and

Richard J. Lewis. New York: Van Nostrand Reinhold Company. Hofenk de Graaff, Judith. (2004). The Colorful Past. Origins, Chemistry and Identification of Natural

Dyestuffs. London: Archetype. Kidd, Kenneth E. 1979. Glass Bead-Making from the Middle Ages to the Early 19th Century. History and

Archaeology 30. Hull, Quebec: Canadian Government Publishing Center. (pp 8-16 & 49-68) Koestler, R.J; Sheryll, R; and Indictor N. 1985. Identification of Dying Mordants and Related Substances

on Textile Fibers: A Preliminary Study Using Energy Dispersive X-ray Spectrometry. Studies in Conservation, 30. London: James & James. (pp 58-62)

Mills, John S. and White, Raymond. (2003) The Organic Chemistry of Museum Objects. New York:

Butterworth-Heinemann.


Peranteau, Anne. 2003. A Technical Study of Two 17th Century English Embroideries. Winterthur

Museum Department of Art Conservation. (pp 1-9) Quye, Anita and Wouters, Jan. 1992. An Application of HPLC to the Identification of Natural Dyes. Dyes

in History and Archaeology 10. Papers presented at the 10th annual meeting, York. York: Textile Research Associates. (pp 48-54)

Saltzman, Max. 1986. Analysis of Dyes in Museum Textiles or, You Can’t Tell a Dye by Its Color. Textile

Conservation Symposium in Honour of Pat Reeves. Eds. C.C. McLean and P. Connell. Los Angeles: Los Angeles County Museum of Art. (pp 27-39)

Smithsonian Museum of American History. The Price of Freedom: Americans at War. Exhibition. Dec.

2004. (Catalog # 17090, Accession # 60666) http://americanhistory.si.edu/militaryhistory/collection/object.asp?ID=325 (12/12/04)

Schweppe, Helmut. 1989. Identification of Red Madder and Insect Dyes by Thin-Layer Chromatography.

Historic Textile and Paper Materials II: Conservation and Characterization. S. Haig Zeronian and Howard L. Needles, eds. Washington, D.C: American Chemical Society. (pp 188-219)

Tímár-Balázsy, Ágnes. 2000. From Test-tubes to 3D Fluorescence Spectra. Textiles Revealed: Object

Lessons in Historic Textile and Costume Research. Mary M. Brooks, ed. London: Archetype Publications. (pp 143-148)

Tímár-Balázsy, Ágnes and Eastop, Dinah. 2002.Chemical Principles of Textile Conservation. New York:

Butterworth-Heinemann. Wakefield Family History Sharing. War Slang. Updated Sept. 30, 2004.

http://www.wakefieldfhs.org.uk/War%20Slang.htm (12/12/04) Wills, Geoffrey. 1965. English Looking-glasses. A Study of the Glass, Frames and Makers (1670-1820).

London: Country Life. (pp 60-64) Weissman, Judith R. and Lavitt, Wendy. 1987. Labors of love. America’s Textile and Needlework, 1650-

1930. New York: Alfred A. Knopf. Witnall, Robert; Clark, Robin J.H; Cooksey, Christopher J, and Daniels, Marcus A.M. 1992. Non-

Destructive, in situ Identification of Indigo/Woad and Shellfish Purple by Raman Microscopy and Visible Reflectance Spectroscopy. Dyes in History & Archaeology 11. Papers presented at the 11th annual meeting, York. York: Textile Research Associates. (pp 19-24)

VIIa. Working bibliography Berni, Ralph J; Tripp, Verne W; and Hebert, Jacques J. 1984. X-ray Diffraction and Fluorescence.

Analytical Methods for a Textile Laboratory. J. William Weaver, ed. Research Triangle Park, N.C: American Association of Textile Chemists and Colorists. (pp 293-311)

Cazenobe, Irene; Bacci, Mauro; Picollo Marcello; and Radicati, Bruno. 2002. Non-Destructive

Spectroscopic Investigation of Dyed Textiles: an Application to Yellow Dyed Wool Samples. Preprints, 13th Triennial Meeting, Rio de Janeiro, 22-27 September 2002, ICOM Committee for Conservation. London: James & James. (pp 238-244)

Dean, John A. (1999). Lange’s Handbook of Chemistry. New York: McGraw-Hill. Greaves, P.H. 1995. Scanning Electron Microscopy. Microscopy of Textile Fibres. Oxford: BIOS Scientfic

in Association with the Royal Microscopical Society (pp 51-67) Járó, Márta. 1993. Genuine or False? Investigation of Metal-printed Textiles Dated to the 11-15th

Centuries. Preprints, 10th Triennial Meeting, Washington, D.C, 22-27 August 1993, ICOM Committee for Conservation. Paris: Allen Press.

Járó, Márta. 1984. The Investigation od the Metal Thread Embroidery Threads of the Hungarian

Coronation Mantle by Scanning Electron Microscope and Physical Methods of Analysis. Preprints, 7th


Triennial Meeting, Copenhagen, 10-14 September 1984, ICOM Committee for Conservation. Paris: ICOM and J. Paul Getty Trust.

Járó Márta; Gál, Tamás; and Tóth, Attila. 2000. The Characterization and Deterioration of Modern Metallic

Threads. Studies in Conservation, 45. London: James & James. (pp 95-105) Mass, J.L. 1999. Instrumental Methods of Analysis Applied to the Conservation of Ancient and Historic

Glass. The Conservation of Glass and Ceramics: Research, Practice, and Training. N.H. Tennent, ed. London: James & James. (pp 15-41)

Schreurs, J.W.H & Brill, R.H. 1984. Iron and Sulfur Related Colors in Ancient Glasses. Archaeometry 26,

vol. 2. (pp 199-209) Tímár-Balázsy, Ágnes and Eastop. 2002. Chemical Principles of Textile Conservation. New York:

Butterworth Heinemann. (pp 381-405) VIII. Acknowledgements The author would like to thank the following people for help during the time of examination and when writing this report.

Catherine Matson, Assistant Scientist, Winterthur Museum

Jennifer Mass, Scientist, Winterthur Museum Joseph Weber, Assistant Professor, University of Delaware Janice Carlson, volunteering scientist, Winterthur Museum Chris Peterson, volunteering scientist, Winterthur Museum

Richard Newman, Head of Scientific Research, Museum of Fine Arts, Boston Debbie Hess Norris, Chair Art Conservation Department, University of Delaware.

Margaret Little, Associate Object Conservator, Winterthur Museum Joy Gardiner, Textile Conservator, Winterthur Museum

Kathleen Kiefer, Associate Textile Conservator, Winterthur Museum Linda Eaton, Textile Curator, Winterthur Museum

Allison McCloskey, Graduate Textile conservation student, Winterthur Museum Kate Sahmel, Graduate Textile conservation student, Winterthur Museum

Anne Peranteau, Mellon Fellow in Textile Conservation, Philadelphia Museum Class of 2006

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