34,100 research outputs found
Folder 40: Kusko, B.H. and S. Colinart. Analyse des Pigments “A la Momie” par la Méthode PIXE, 1988-1989
No full textThis folder contains various versions of a typewritten report: Kusko, Bruce H., and Sylvie Colinart. "Analyse des Pigments 'A la Momie' par la Méthode PIXE." Rapport d’Activité 1988-1989. Service de Physique, LRMF Most of the text is written in French.The items in this folder are part of the Thomas A. Cahill Papers--Crocker Historical and Archaeological Project, 1981-2009. They are from Series 1: Thomas A. Cahill Research Papers, 1981-1994. This series consists of various research papers and published articles based upon Dr. Cahill's research using Particle Induced X-ray Emission (PIXE) techniques in analyzing inks and papers
Folder 34: Kusko, B.H. Cyclotron Analysis of the Paper and Ink Reveals the Secrets of the Written and Printed Word, 1988
No full textThis folder contains an entire issue of a journal containing the published article: Kusko, B. H. "Cyclotron Analysis of the Paper and Ink Reveals the Secrets of the Written and Printed Word." _Literary Research: A Journal of Scholarly Method and Technique_ 13: 2&3 (1988): 123-136. The folder also contains two photocopies of the article as well as a typewritten manuscript of the article and correspondence with the publisher. The journal issue and duplicate article photocopy have not been digitized and are not represented here.The items in this folder are part of the Thomas A. Cahill Papers--Crocker Historical and Archaeological Project, 1981-2009. They are from Series 1: Thomas A. Cahill Research Papers, 1981-1994. This series consists of various research papers and published articles based upon Dr. Cahill's research using Particle Induced X-ray Emission (PIXE) techniques in analyzing inks and papers
Folder 59: Kusko, Bruce H. The Analysis of High-Temperature Acclerant Fire Debris using PIXE, 1992
No full textThis file contains a typwritten version of a report: Kusko, Bruce H. "The Analysis of High-Temperature Acclerant Fire Debris using PIXE". Report to Richard Gelhausen and Dennis Fowler, Fire Investigator, Seattle Fire Department.The items in this folder are part of the Thomas A. Cahill Papers--Crocker Historical and Archaeological Project, 1981-2009. They are from Series 1: Thomas A. Cahill Research Papers, 1981-1994. This series consists of various research papers and published articles based upon Dr. Cahill's research using Particle Induced X-ray Emission (PIXE) techniques in analyzing inks and papers.«;~,dm!~ijt'rif41 aab ~re~aeo"8if41~r08ram
Crocker Nuclear Laboratory
University of California, Davis
Davis, CA 95616
Richard Gelhausen
Dennis Fowler
Seattle Fire Department
301 Second Avenue South
Seattle, WA 98104
Dear Rich and Denny,
Iam sending you an interim report on the cyclotron analysis of samples from
suspected high temperature accelerant fires. It is still really a draft, and it rambles at times,
but Iknow you need something now, so here it is. Please send it around to others for
conunents, criticisms, and suggestions. Iwould like the feedback to write a good report, so
we can show that this method is worth pursuing. Thanks for being patient.
June and July will be busy months for me (which aren't?), so I will not have much
time to work on it until August. But feedback is welcome anytime.
Sincerely,
Dr. Bruce H. Kusko
Group Leader, CHAP
encl.
cc. T.A. Cahill
High Temperature Accelerant Fire Debris: Samples Analyzed by PlXE
Draft Report
Introduction
Over the past (10) years there have been (6 -91) building fifes in the Pacific
Northwest suspected to be the work of an experienced arsonist using special materials.
These fires reached temperatures of 3000 degrees F, yet many buildings were empty so
the "fire load" was only the building itself. What little was there either melted or was
vaporized. Fire investigators have yet to fwd conclusive evidence in the building debris
of the fuel or oxidant used, yet the physical effects of the fire are evidence enough to
class them as high temperature accelerant, or HTA fires.
We were asked by investigators of the Seattle Fire Department to help them with
their forensic study. They are already getting the help of other regional and federal crime
laboratories, University laboratories, and laboratories in private industry, but firm results
have been elusive. It is suspected that the high temperature accelerant is a mixture of a
metallic fuel and a solid or liquid oxidizer.
A number of small and large-scale test fires have been conducted and the mixture
that came the closest to reproducing the characteristics of the suspected HTA fires was
aluminum (powder and turnings) and ammonium nitrate or ammonium perchlorate as the
oxidant (all bound together in gasoline or diesel fuel).
Of course, any number of metals could be used as a fuel, including Li, Be, Na,
Mg, AI, K, Ca, Ti, V, Zn, Zs, and even U. Potential solid oxidizers include nitrates,
chlorates, chromates, and oxides. Since the possibilities are quite numerous, it was
thought that PIXE would be a good method to try. PIXE is a multi-elemental technique,
sensitive to all elements above Na on the periodic table if they are present in major, minor
or trace amounts. In addition, PlXE is non-destructive, relatively rapid, and sensitive to
surface composition. The beam-in-air PIXE system at CNL allows us to analyze even
large and bulky pieces of debris. It was hoped that PIXE could be used to identify some
of the chemical elements remaining from the fuel-oxidant-binder mixture.
The materials brought to CNL for testing consisted of burned concrete, melted
metal, charred wood, carpet remnants, and plastic bucket bottoms with residue of perhaps
the fuel-oxidant-binder mixture. Debris from the large scale test burn was used as contol
samples.
The PIXE system was arranged to optimize the sensitivity for the elements in the
range Ca to Pb. We also tested a new technique called PIGME, used to detect gamma-rays
emitted during proton bombardment. This technique is sensitive to elements
impossible or very difficult to detect with PIXE, (such as Li, Be, Na, Mg, and AI).
Unfortunately PIGME did not work properly and no information was obtained at this
time. We thus did not obtain information on AI, Mg, Na, Li, or Be.
Nothing obviously unusual was detected with PIXE, but the data is being
scrutinized by forensic scientists for clues. There were differences between clean and
burned concrete; burned concrete usually had excess Fe, Cu, Zn, and Pb; burned wood
also picked up inorganic materials. The fact that certain suspected elements were not
found is also useful information. All this is now being combined with other HTA data,
and it is hoped that a clearer picture of the arsonist is forthcoming.
Methods
We used the standard CHAP proton milliprobe, or beam-in-air PIXE system (for
the first time in ahnost 3 years) (designed for books and other flat objects.) It was fairly
easy to orient any piece, large or small, in the proton beam. A schematic of the milliprobe
is shown in figure 1.
Beam size was 2 mm x 3mm diameter. Beam currents were not measured but
were typically 10 - 20 nanoamperes. Analysis times were 5 minutes (twice as long as a
standard run, giving 1.5 times better sensitivity.
A 1 mil Kapton filter was placed over the detector to attenuate the low energy X-rays,
allowing us to use higher beam currents than usual (3 - 5 na). This also increased
our sensitivity to the other elements (> Ca). But this meant that the elements Na, AI, and
Mg were not detected. A typical spectrum is shown in figure 2.
Dennis Fowler brought 60 specimens (pieces of evidence) to Davis on April 23.
[See table 1.] About half (31) of these samples were analyzed. Since our method is
comparative, we tried to find (or make) a clean surface to analyze along with the burned
surface. Replicate measurements were made on 23 of the samples, resulting in 61
separate analyses.
Results
Results are given in Tables 2a -2e. Values are uncorrected, meaning that even
ratios of elements are not correct. {We can still compare data within this set ofPIXE
results.} [The problem is solvable in theory, but we did not run enough "standards" in
order to recalculate the cross-section table.]
Since beam current was not being measured during each run, (the sample stops
the beam) we had occasional problems with overload, resulting in "live times" of less
than 20%. At other times the beam current was much too low, and not enough charge
was accumulated. These runs need to be looked at carefully.
The elements commonly found included S, K, Ca, Ba or Ti, Fe, Cu, and Zn, and
occasionally, Si, CI, Cr, Ni and Pb. Comparisons of burned versus unburned concrete,
for example, shows elemental differences, attributable to the fire, and perhaps linked to
the accelerant used. Nothing obvious stands out, but the data are being examined
carefully for clues.
Conclusion
PIXE was used to analyse debris from high temperature fires. A lot of information
was obtained, and the data are being evaluated. A formal report is being prepared.
Bruce H.Kusko
Crocker Nuclear Laboratory
University of California
Davis, CA 95616
June 7, 1992
\" o.~\eI HTA Arson Sample Inventory
Arson Samples U.C.Davis PIXE Anal"sis April23.24 1991
Fire Matertal Sample Description rN--u-m-b-e-r -R-un--n-o.--
1.0. analyzed
Puvallup Test Fire Metal PA molten AI - -
Puyallup Test Fire Metal PB Cu wire - ----- Puyallup Teat Fire Metal PC steel bucket bail - -
Puyallup Test Fire Metal PO molten brase - -
Puvallup Test Fire Metal PE Cu - -
Puvaltun Test Fire Metal PF Steel? - -
Puvallun Test Fire Metal PG Cu - -
Puyallup Test Fire Metal PH molten AI 3 309-311
Puyallup Test Fire Metal PI melted steel tubing/chrome platec 2 319,320
Puyallup Test Fire PK Explosive residue -1---4--- 3-1-5--3-18-- PuvallUDTest Fire PJ Assorted stuff 3 312-314
Artificial Ice Concrete AI-1 Floor 2 353354
Artificial Ice Concrete AI-2 Floor 2 355,356
Blackstock Lumber Wood B5-1 chips 4 347-350
Blackstock Lumber Metal 85-2 slag 3 344-346
~_kstock Lumber Metal 1,B15--3 ----~9. _______ - -1-------
Blackstock Lumber Metal ,B5-4 slag - -
Brock Candles Metal BC-1 melted metal 2 374375
Brock Candles Wood - BC-2 charred wood 1 376
Cal Wood Concrete CW-1 Wall 2 336,337
Cal Wood Concrete CW-2 Floor 2 340341
Cal Wood Concrete ---C-W--3--- 1Fl-o-o-r ------- 2 -33-8-,339 Cal Wood Concrete CW-4 Floor (Control) - -
Cal Wood Concrete CW-5 Floor - -
Cal Wood Concrete CW-6 Blister from wall - -
Cal Wood Concrete CW-7 Blister from wall ------- --------- Cal Wood Concrete CW-8 Cooked red 1 379
Cal Wood Concrete CW-9 Wall 1 380
Cal Wood Wood CW-10 Charcoal in metal 1 381
------ ----- ---------
Carpet Exchange Metal CE-1 slag 1 335
--- 1------- -c------ -------- Golden Ox Concrete GO-1
Golden Ox .__ .- Metal GO-2 melted AI + char 2 char 377 378
Golden Ox Metal GO-3 AI leg of metal desk - -- -
- -------
Hansen Fruit Warehou Metal HF-2b debris - -
Hansen Fruit Warehous Metal HF-2c wire - -
Hansen Fruit Warehou-1-1 T-1-1 BS-1-2 BS-1-3A BS-1-4A HF-3A-1 HF-3A-2 AI-1-1 AJ-1-2 AI-2-1 AI-2-2
Description metal metal metal wood wood wood wood residue residue concrete concrete concrete concrete
cleaned burned burned away towards away towards ? ? clean burned clean burned
Silicon •
IPhos~lhorus
:Sulfur .• 0.11 0.62 0.09 1.5 0.71 2.1 0.43 0.8 1.2
Chlorine • 83 11.9 2.6
,Argon • 1.63 3.9 2.56 48.2 56.8 50.2 31.7 33.3 23 16.7 13 16.6 16.2
IPotass;ium*
(::alciulTI 0.63 1.7 3.6 156 290 162 226 392 152 1970 1520 1580 2150
Titanium 0.38 0.54 0.61 4.4 4.5 22 1.3 0.083 0.38
IBariurn 2.6
Chromium 0.17 0.021 0.12 0.54
IManga.nese 0.45 0.55 1.4 0.38 4.3 0.034 0.078 0.088
llron 75 78 74 9.9 0.42 11 0.078 24 44 4.6 5.9 2.6 4.4
Co~per 0.021 0.092 0.021 0.028 6.7 7
INickel 0.021
;Zinc 9.2 5 0.056 0.67 0.028 0.085
Strontium 0.078 0.074
ILead 0.71 0.19 0.092
.Au 0.15
ILive Time 87 86 86 19 35 31 18 65 72 80 82 83 78
Cha!llE~ 15 33 19 464 431 397 410 311 181 53 54 60 55
page 4
Arson samples U.C.Davis PIXE analysis
IApril 23. 24 1991 Uncorrected data
Run no. 357 358 359 360 361 374 375 376 3n 378
sample no. VB-1-1 VB-1-2 VB-2-1 PW-2 PW4 BC-1-1 BC-1-2 BC-2-1 00-2-1 G0-2-2
Description concrete concrete metal metal wood metal metal wood wood wood
clean burned burned char burned burned char char char
Silicon *
Phosphorus
Sulfur * 0.36 0.9 2 1.6
Chlorine *
Argon * 14.1 11.3 12.3 3.33 26.3 1.28 1.59 5.03 44.4 16.3
Potassium* 14.6
Calcium 1530 1320 1330 14 1470 5.5 4.8 238 782 1550
Titanium 0.5 0.52 0.16 0.54 0.52 0.9 0.5 7.8
Barium
Chromium 0.029 0.028 0.33
Manganese 0.023 0.008 0.78 1
Iron 14 17 7.1 82 0.91 n 88 56 0.51 2.1
Copper 2.7 0.16 0.15 0.15
Nickel 4.3 7.6 1.7
Zinc 0.51 0.51 0.56 0.14 0.32 0.73 0.64
Strontium 0.18
Lead 0.1 0.43
Live Time 80 82 84 86 rr 86 85 85 34 69
Charge 43 27 42 13 97 16 12 79 836 311
page 5
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Folder 41: Kusko, B.H. and J. P. Rioux. Analyse des Pigments de “La Vierge et l’Enfant” par la Méthode PIXE en Faisceau Extrait, 1988-1989
No full textThis folder contains three copies of a typewritten report: Kusko, Bruce H., and J. P. Rioux. "Analyse des Pigments de 'La Vierge et l’Enfant' par la Méthode PIXE en Faisceau Extrait."
Rapport d’Activité 1988-1989, Service de Physique, Laboratoire de Recherche des Musees de France, Paris, April, 1989. Only one copy has been digitized and is presented here.The items in this folder are part of the Thomas A. Cahill Papers--Crocker Historical and Archaeological Project, 1981-2009. They are from Series 1: Thomas A. Cahill Research Papers, 1981-1994. This series consists of various research papers and published articles based upon Dr. Cahill's research using Particle Induced X-ray Emission (PIXE) techniques in analyzing inks and papers.ANALYSE DES PIGMENTS DE "La Vierge et l'Enfant"
PAR LA METHODE PIXE EN FAISCEAU EXTRA IT
Bruce H. Kusko, J.-P. Rioux
Apres avoir montre les possibilites de la methode PIXE pour l'etude des pigments purs, nous
avons entrepris d'analyser les pigments du tableau "La Vierge et l'Enfant" avec le faisceau extrait.
Les conditions d'analyse ont ere choisies de facon a respecter parfaitement l'integrite du
tableau: courant de protons de faible intensite (200 a 300 pA), refroidissement par ventilation au
niveau du point d'impact, limitation du temps d'analyse a moins de cinq minutes.
Les resultats quantitatifs ont ete determines au moyen du logiciel PIXAN. Les elements legers,
en particulier l'oxygene et le carbone, n'etant pas analyses, les concentrations absolues ont ete
calculees a partir des stoechiometries probables en supposant la somme egale a 100%. Les resultats
sont donnes dans les tableaux 1 et 2. Les erreurs experimentales sont de 10 a 20 %.
Resultats et discussion
Les resultats du PIXE (1,2) concordent bien avec ceux du rapport etabli au LRMF en 1975
(3,4). Ils ont montre que non seulement le tableau n'est pas du Xveme siecle, mais qu'il ne peut etre
anterieur a la fin du XtXeme.
L'analyse de la couche mince presente au dessous de la couche d'or et du pigment a ete fai~ a
un endroit ou la couche d'or est ecaillee. Cette couche mince se compose d'un melange a parts egales
de sulfate de baryum et de sulfure de zinc, connu sous le nom de lithopone. Elle contient aussi du fer
qui indiquerait la presence de bol,
Plusieurs des pigments que nous avons trouve ne sont pas du Xveme siecle, par exemple le
jaune d'antimoine (ditjaune de Naples) et le rouge de cadmium.
Conclusion
Des etudes complementaires sont necessaires afin de mieux connaitre les possibilites
d'application a l'etude des tableaux du PIXE en faisceau extrait. Cette etude montre deja certains
avantages du PIXE, notamment sa rapidite: les resultats presentes ici ont ete acquis en quelques
heures. Cette methode ne necessite aucun prelevement, elle permet d'analyser une large gamme
d'elements avec une grande sensibilite. Le PIXE, et les autres techniques d'analyse par faisceau
d'ions, representent un precieux moyen d'ameliorer la connaissance de notre patrimoine culturel.
References:
(1) B.H.Kusko, Compte rendu, Bourse Fulbright, 1988-1989.
(2) B.H.Kusko, M.Menu, T.Calligaro, J.Salomon, PIXE at the Louvre Museum, presente au
Verne conges PIXE, Amsterdam, aoiit 1989.
(3) LRMF, Ecole siennoise - Xveme siecle (?) Madone, Etude de 1a matiere picturale, Musee
du Louvre INV 20642.
(4) LRMF, La Vierge et l'Enfant, La vie mysterieuse
Folder 43: Cahill, T.A., R.A. Eldred, B.H. Kusko, D. Dutschke, R.N. Schwab, G. Möller, and A. Pooley. Comparison of PIXE Microprobe and Removed Microparticle…, 1989
No full textThis folder contains three copies of an abstract of a conference presentation: Cahill, Thomas A., R. A. Eldred, B. H. Kusko, D. Dutschke, R. N. Schwab, Greg Möller, and Alan Pooley. "Comparison of PIXE Microprobe and Removed Microparticle Analyses of the 'Vinland Map'." Presented at the Fifth International PIXE Conference, Amsterdam, August 25-30, 1989. Only one copy has been digitized and is presented here.The items in this folder are part of the Thomas A. Cahill Papers--Crocker Historical and Archaeological Project, 1981-2009. They are from Series 1: Thomas A. Cahill Research Papers, 1981-1994. This series consists of various research papers and published articles based upon Dr. Cahill's research using Particle Induced X-ray Emission (PIXE) techniques in analyzing inks and papers.PIXE V, VU, AMSTERDAM.
Abstract form.
COMPARISON OF PIXE MICROPROBE AND REMOVED
MICROPARTICLE ANALYSES OF THE
"VINLAND MAP"
Thomas A. Cahill, Robert A. Eldred, Bruce H. Kusko*, Dennis
Dutschke, Richard N. Schwab, Greg Moller, and Alan Pooley**
Crocker Historical and Archoeological Projects,
Crocker Nuclear Laboratory,
University of California, Davis, CA 95616 U.S.A.
The "Vin1and Map", discovered in the 1950s, was thought
for two decades to be the first map to show part of North
America at a pre-Columbian date around 1440 A.D. However,
optical and X-ray analyses of micropartic1es removed from the
map in 1974, were interpreted as proof that the map was a 20th
century fake. Our re-ana1ysis of the map in 1987 showed the
prior "proof" to be erroneous, and opens once again the map to
serious study. This paper will describe the differences
between the two approaches and the present state of the
controversy.
***
AGLAE, Lourve Museum, Paris, France
Peabody Museum, Yale University, New Haven, Connecticut
I.
t:./3
-
Folder 54: Cahill, T.A., B.H. Kusko, R.A. Eldred, and R.N. Schwab. Compositional Comparison of the Mark Hoffman “Oath of a Freeman” and the “whole Booke of Psalmes", 1991
No full textThis folder contains an offprint of a published article: Cahill, T.A., B.H. Kusko, R.A. Eldred, and R.N. Schwab. "Compositional Comparison of the Mark Hoffman 'Oath of a Freeman' and the 'Whole Booke of Psalmes'. _The Judgment of Experts: Essays and Documents about the Investigation of the Forging of The Oath of a Freeman." Edited by J. Gilreath. American Antiquarian Society, 1991. Pages 75-96.The items in this folder are part of the Thomas A. Cahill Papers--Crocker Historical and Archaeological Project, 1981-2009. They are from Series 1: Thomas A. Cahill Research Papers, 1981-1994. This series consists of various research papers and published articles based upon Dr. Cahill's research using Particle Induced X-ray Emission (PIXE) techniques in analyzing inks and papers.Compositional Comparison of the Mark Hoffman "oath of a Freeman" and the
~ole Book of Psalms."
T.A. Cahill, B.H. Kusko, R.A. Eldred, and R.H. Schwab
Crocker Historical and Archeological Projects (CHAPS), University of
California, Davis 95616
The Mark Hoffmann "Oath of a Freeman" and the "Whole Book of Psalms" were
analyzed by the external proton milliprobe at the Crocker Nuclear Laboratory,
University of California, Davis for elemental constituents of the paper and
ink. These analyses were supported by Mr. Justin Schillet of the
Schiller-Wapner Galaries, New York, with the collaboration of E. Dunlap of the
Rosenbach Library, Philadelphia, who supplied the "Whole Book of Psalms". The
purpose of these analyses was to compare the documents in order to bring
compositional data to bear on the authenticity of the "oath". In this
article, we will give a little background to the analyses, reproduce the
original report in its entirety, and then comment on the results with
knowledge of events.
Proton Milliprobe Techniques
The proton milliprobe technique at Davis is a refinement of the technique
of Proton Induced X-ray Emission (PIXE) designed to generate quantitative
composition data on fragile objects without any harm. The 4.5 MeV proton beam
for the Crocker Cyclotron passes through the paper and ink generating
Cahill et ale
characteristic X-rays that reveal the mass and type of elements silicon and
heavier (Figure 1). Sensitivities are generally about 1 part per million,
while accuracy and precision are about ±S absolute. Each analysis covers an
area of between 0.5 mm2 and 3mm2, depending on the task.
A few points must be noted. Since the data reveal only elemental
composition, chemical states are not revealed. Thus, the iron in Fe203 cannot
be told from the iron in Fe02. Secondly, the ink must be analyzed with the
substrate, as shown in Figure 1. Thus to obtain .the composition of the ink,
one must subtract the result of the "substrate only'; from that of "substrate
plus ink". For some elements, this is easy, but in the best cases, a severe
loss of sensitivity ensues. In the worst case, in which there is a large
amount of a given element in the substrate, the "ink alone" values are quite
insensitive. Finally, all results are merely comparisons. No dates are
involved. Thus, for those periods in which many documents are available for
comparisons puposes, such as the Incunabula Period of printing, a high degree
of confidence can be attained. For others, such as the first years of the
Stephen Daye press in Cambridge, little is available for comparisons' sake.
This latter problem is compounded by the diverse sources of Stephen Daye's
paper, originally from England in multiple batches, which make paper
comparisons quite complicated.
with this background of the method, both documents were tested by the
CHAPs tearn at Davis during the afternoon and early evening of April 17, 1986.
The preliminary report of those analyses follows.
Fi gure I
Faraday Parchment C/
4.5 MeV
Proton 8ea~ <=_---,..r- ~-_- .•_'~_ZZ-_~~_2Cg~~~:_/
HeNe
Laser
X-ray
Detector
"'-- ~ To Computer
April 28, 1986
Preliminary Report on the Comparision
../ of the "oath of a Freeman" and the
"Bay of Psalm Book"
by
B. Kusko, T. cahill, R. Schwab and R. Eldred
The Crocker Historical and Archaeological Project
Crocker Nuclear Laboratory, Univ. of California, Davis, CA 95616
On April 17, 1986, two documents, the "oath of a Freeman", from J. Schiller
of the Schiller-Wapner Galleries, NY and the "Whole Booke of psalmes",
E. Dunlap, Rosenbach Library, Philadelphia, were analyzed by PlXE on the exter-nal
proton milliprobe of the CHAPs group, Crocker Nuclear Laboratory.
For a description of the procedures and quality assurance protocols, see
Appendix~. For this run, several standards were used: 1) Pb foil, CUS foil
(both from Micromatter, Inc., WA) 2) NBS thin film standard 1607, and the 1180
AD Manuscript (TAC) previously analyzed on almost every CHAPSs run since 1978.
Agreement was excellent, and no normalization correction had to be applied (RE-NORM
~ 1.000). The beam spot was set to 1.5 x 1.S rom,giving a 1.S x 2.1 rom
spot on the documents.
Twenty analyses were made on the "oath of a Freeman" (see Figure 1). Since
the paper, ink, and verso manuscript inscription were very similar at all
points, we proceeded to analyze the "Bay of Psalm Book".
Twenty two analyses were made of the "Whole Booke of Psalmes". These in-cluded
a paper and paper-pIus-ink analysis for the 5 major paper types, the fac-simile
pages, the two end papers, and front and back covers of the Book.
An early analysis of the paper and ink is shown in Table 1. All data have
been corrected for x-tay attenuat}on by the code IPAPA (REA), and results are
given in absolute units (ng/cm). The data are presented for the major paper
types, for comparison with the "oath of a Freeman". As can be seen, the "Oath",
while appearing to contain old (pre 1830) paper similar to others analyzed at
Davis, differs sharply from every type of paper in the Bay of Psalm Book.
The lack of S, Cl, K, and Hg in the oath paper are significant, as is the
presence of Pb. The Bay of Psalm book paper contains large amounts of S, CI,
and K, and does not contain pb but has Hg. The elements Si, Ca, Mn, Fe, CU, and
Zn are found in varying but comparable amounts in the two documents.
April 28, 1986
The printing inks of both documents were similar in having only trace am-ounts
of any element above silicon on the periodic table, and therefore 20stly
carbon based. Both inks showed significant amounts of Pb (100-200 ng/cm ) and
traces of Fe.
The manuscript ink on the verso of the oath of a Freeman contained large
amounts of Fe, as well as P, K and Cl. This is typical of iron-gall ink, a corn-mon
manuscript ink used since the 1100's.
Summary
The dramatic differences in the papers of the "oath of a Freeman" and "Bay
Psalm Book" clearly indicate a different paper type. The very low values of S,
Cl, and K are unusual but not unique in our studies of pre~1830 papers. Some
examples of other papers are given in the appendices, but nonJ~particularly re-levant
to the present papers.
We do not mean to imply that the oath is either a forgery or authentic,
just that different paper was used. The printer may in fact have used different
paper when. printing this broadside as opposed to the book, and we have only a
very limited number of documents ·to compare.
The ink used in both documents appears to be carbon-based, containing small
amounts of Pb. The ink used in the Oath may also have n.ft Ti. They are neither
unusual nor statistically different from each other, and it is possible they are
from the same source. Again, we have very few inks of the period for compari-sian,
and carbon based inks with trace impurities are found routinely in many
documents.
April 28, 1986
Appendices
1. Original record of analyses for the "Oath of ~ Freeman" and Bay Psalm
Book
2. Results of Elemental analyses for both documents
3. Description of the Davis PIXE milliprobe from "the Calov Bible of
J.S. Bach"
4. Examples of various papers-a)
18th through 19th century
b) Incunabula period, 15th century
c) the Calov Bible of J.S. Bach, German 17th century
Tabl!! 1
COMPARARTIVE ELEMENTAL COMPOSITIONS OF PAPER AND INK
( ng/cm2 ; corrected for absorbtion by IPAPA )
E;i 1 icon
< Si )
PAPER
Oid~_h of a
Fr-f.:lf?Ill,:\r1
(t1E?an ± a )
14, ::::'00
± 4 ~500
F'tlCl'sptlCll- us; < I , ~500
(P)
Su If ttr:
(E))
ell I01- i ne
([;1 )
F'Clta~;5i um
(V)
Calcium ( c:.:\ )
TiLan ium
eli )
M,3nqanese
("In)
I1'-- on
(Fe)
Copper--
(eu)
Zinc
(Zn)
t-Ier cur- y
CHq)
L._ead
(Pb)
<400
< ~)()()
<200
1~::'.190
± 2, ~140
< 75
:1,2::25
± ~::'10
± 1:?
199
± 4~i
< 25
~.?6B
± 291
D6~)
± 140)-{'
INK
Bay Psalm
BODk
(t-1.3:: / t'1i n )
Oath of a
Freeman
(print) <writing)
B,"':\y F'salm
BODk
(pr- i n+ )
.16
500
t 1. an al va ia deletr.",d ** 5 (Jut C)-f "1 analv ses when lead \l'la5 found
Values marked with a _have a standard deviation as large as the values given.
2(~, 7001
< 4 ~500
..,~ 4-,900
4B~500/
:l9~OOO
:?2~500/
2,080
R30
7,490/
~)!f 5~t2()
1~:~r,600/
B,7:l0
NA - 140 190
2,2BO/
~'?:~:6
60
::~;~720/
1~290
- -11-00 .19, 600
10:?/
tEl
261/
1:13
:::.~ 1:::'0/
298
1~)5/
< ~?5
- :?70
1. 19B1 Cahill, T.A., B. Kusko and R.N. Schwab. Analyses of inks and papers
in historical documents through external beam PIXE techniques,
Nuclear Instruments and Methods 1B1 205-20B.
2. 19B1 Schwab, R.N., T.A. Cahill, B.H. Kusko. "The Cyclotron and
Descriptive Bibliography: A Progress Report on the crocker
Historical and Archaeological Project at Davis" The Quarterly
Newsletter, The Book Club of California, 42 3-12.
3. 19B1 Cahill, T.A., C.G. Higgins and S. Howard. Accelerator-based methods
for fingerprinting marble: A preliminary report. The B3rd General
Meeting of The Archaeological Institute of America.
4. 19B3 Eldred, R.A. External beam PIXE programs at the University of
California, Davis. IEEE Transaction on Nuclear Science,
NS-30:1276-1279, Seventh Conference on the Application of
Accelerators in Research & Industry, North Texas University, (invited
paper).
5. 1983 Schwab, R.N., T.A. Cahill, B.H. Kusko, and D.L. wick. Cyclotron
analysis of the ink in the 42-line bible. The Papers of the
Bibliographical Society of America. 77:3 285-315.
6. 1984 Cahill, T.A., B.H. Kusko, R.A. Eldred and R.N. Schwab, Gutenberg's
inks and papers: non-destructive compositional analyses by proton
milliprobe. Archaeometry, 26:1 3-14.
7. 1984 Eldred, R.A., B.H. Kusko and T.A. Cahill. The external PIXE
milliprobe at Davis: Laser alignment, PIXE calibration, and quality
assurance, Nuclear Instruments and Methods, B3, 579-5B3.
8. 1984 Kusko, B.H., T.A. Cahill, R.A. Eldred and R.N. Schwab. Proton
milliprobe analyses of the Gutenberg Bible. Nuclear Instruments and
Methods, B3, 689-694.
9. 1984 Howard S., T.A. Cahill, N. Herz, C. Higgins, E. Kinmoth and
B.H. Kusko, Computer-assisted accelerator-based methods of
determining the provenance of ancient marbles, presented at the
second Conference on Automatic Processing of Art History Data, Pisa,
Italy.
10. 1984 Bliss, A.S. cyclotron analysis and a fake gospel lectionary of 1328.
Scriptorium, International Review of Manuscript Studies XXXVIII, 2.
11. 1985 Schwab, R.N., T.A. cahill, R.A. Eldred, B.H. Kusko and D.L. Wick, New
evidence on the printing of the Gutenberg Bible, Papers of the
Bibliographical Society of America, 79:3, 375-410.
12. 1985 Almquist, H.J., Color of the Ledger Lines of the Large Numerals issue
of Mexico, 1887. The American Philatelist, vol 99, pp.241-2.
13. 1985 Kusko, B.H, Proton milliprobe analysis of the hand-penned annotations
in Bach's Calov Bible, in The Calov Bible of J.S. Bach, Howard
H. Cox, ed. Studies in MusIcology, No. 92, UM! Research Press, Ann
Arbor, p 31-106.
14. 1986 Schwab, R.N., T.A. Cahill, B.H. Kusko, R.A. Eldred, D.L. Wick, Ink
patterns in the Gutenberg New Testament: The proton milliprobe
analyses of the Lilly Library copy, Papers of the Bibliographical
Society of America, 80:3, 305-331.
15. 1986 Cahill, T.A., D.W. McColm, B.H. Kusko, Control of temperature in thin
samples during ion beam analysis, Nucl. Instrum. and Methods, B14.
38-44.
16. 1987 Cahill, T.A., R.N. Schwab, B.H. Kusko, R.A. Eldred, G. Moller,
D. Dutschke, D.L. wick and A.S. Pooley. The Vinland Map, revisited:
new compositional evidence on its inks and parchment. Analytical
Chemistry, 59, 829-833.
17. 1987 Kusko, B.H., and R.N. Schwab, Historical analyses by PIXE. 4th Int.
PIXE Conf., Tallahassee FL, 9-13 June 1986. Nucl. Instrum Methods
B22, 401-406.
lB. 1987 Cahill, T.A., The Nuclear Bibliophile: Cyclotron studies of rare
documents. Transactions of the XIvth Congress of the International
Association of Bibliophiles, ed. Stephen Tabor Los Angeles, 1987,
37-50.
19. 1987 Schwab,R.N., The history of the book and the proton milliprobe: an
application of the PIXE technique of analysis. Library Trends,
Summer 19B7, 53-B4.
20. 19BB Kusko, B.H., Cyclotron analysis of paper and ink reveals secrets of
the written and printed word. Presented at a special seccion of the
1987 convention of the Modern Language Association of America,
December 2B, 19B7. To be published in Literary Research.
21. 19BB Cahill, T.A., Gutehberg and the cyclotron. Accepted for publication,
The Library Associates, UCO.
Cahill et al.
Post-Revelation Commentaries
The compositional uniformity of the Mark Hoffman "Oath" is clearly
evident in the results for the paper and ink. Thus, good average values are
obtained, especially for the paper. The inks were harder to evaluate, since
the mass of elements heavier than silicon was so low that the ink was clearly
carbon based. The minor trace elements, derived as we now know from the
combustion of 17th century paper, were of the same magnitude as that in the
printing of the "Bay Psalm Book". The iron-rich manuscript ink looked a
little too clean (i.e. see our results on the "Tartar Relation' (le-)), but we
now know that Hoffman added pure (modern) tannic acid to the inks for the
verse inscription. Processing from oak galls would have added additional
trace elements, yet the results were not outside of the range of other inks of
the period (fb)
The clear and consistent differences between the papers was the strongest
evidence against the "Oath". As was stated in the report, the Oath
".. differs sharply from every type of paper in the "Bay Psalm Book". Yet,
without better knowledge of the paper sources, who can say definitely that
such paper was impossible? In fact, we know that the papers dated for the
17th century, England, but 30 or 50 years later, why were the papers of the
"Bay Psalm Book" so chemically complex? Until we have more examples of this
period, we may never know
Folder 27: Kusko, B.H. Proton Milliprobe PIXE Analysis of the Inks in the Cincinnati Haggadah, 1987-1988
No full textThis folder contains a research report: Kusko, B.H. Proton Milliprobe PIXE Analysis of the Inks in the Cincinnati Haggadah. Report to H. Zafren, Hebrew Union College Library, Cincinnati, May, 1987.The items in this folder are part of the Thomas A. Cahill Papers--Crocker Historical and Archaeological Project, 1981-2009. They are from Series 1: Thomas A. Cahill Research Papers, 1981-1994. This series consists of various research papers and published articles based upon Dr. Cahill's research using Particle Induced X-ray Emission (PIXE) techniques in analyzing inks and papers.UNIVERSITY OF CALIFORNIA, DAVIS
BERKELEY • DAVIS • mVINE • LOS ANGELES • RIVERSIDE • SAN DIEGO • SAN FRANCISCO SANTA BARBARA· SANTA CRUZ
CROCKER NUCLEAR LABORATORY DAVIS, CALIFORNIA 95616
Mr. Herbert Zafr en
Director or Libraries
Hebrew Union College
5 j 0 1 Clifton Avenue
Cincinnati. Ohio 45220-2488
Dear Mr Zatren,
I am pleased to send you the final report on the PIXE analysis of the
Cincinnati Haggadah. I apologize for taking so long. but in the last year a
series of major beam line changes and a new computer system lead to more
than the usual number of difficulties. I finally did all the number crunching
on my home computer.
The purpose of this project was to perform non-destructive tests of the
chemical composition of the parchment, manuscript inks and painted
illuminations in the Cincinnati Haggadah. The results of these analyses are
important to the CHAPs group of scholars, who are studying the history of
the book and early priming in Europe. A second reason for performing this
investigation was to compare the manuscript inks in the Cincinnati
Haggadah with the typographic ink used in the contemnor aneous 42-!ine
U;menherg j Bible.
The method used in-the examination of the Cincinnati Haggadah was proton-induced
x-ray emission, or PIXE, and the tests were conducted with the
beam -in -air proton milliprohe. This analyiical technique is very well suited
for the analvsis of the parchments. inks, and painted illu rninai ions
TI..&)C-lc, .m1.1 ai:nu11s-c...r in!-it j'111,'c...• w'..tI.I e re••••.•����� "d"Ce;t\.e."r",ml.1line.dI U". to he......1;1'-(1_ 11 bo!al r! .;.1•1'.h'<:•.v.. wv,h1ic1•h.•,&...1.. <~ ••:• I-}'-I, ,\\.••.'•i•.•·••,...d _ nLa"\)
re se rnb lance to the priming inks u~~ed in the 4?-iine Hib!e ThE:'clL-H-ed
pj~::n:eDl~ ,\-,'::',e ;JJ~ed 10 be pigments well !~IIO\vn to medieval na.nter s and
illU min a tors.
11 was a privilege to he involved 111 the examination 01 the Cincinnati
Haggadah. If you have any questions about the report Of Jl(:t;U help in
inte.r..p.,reti.n•.g.. It'\ V':"l.ll"y' mate..ri:c..,..::tl, !n~.lle'Ca...s...e. cit'J, _11,'_(1'~, h1_e._s•i•·t. ta.·..tt.v:> fL,'t,.' ~....,.._1·"1"1:•:...,•:...,t·-,\. \1.1.·.t·:' :! "~'.J:qL h!_.._~_,.
lie'a''l'll,j l'):;\l'~ in Ce'f"'l611-1l.. ,".11" ,.'j snen rl ,) .\ 'J',,' ~';l··l,-t. ;1'1" 1\' 1i'f) con ,,::,., "I' ;,'\!~ 'V b u. •.. J. .1..) t' 'I; u~ lit... ~ ~h .•·.!. 'U " ~•.. t;,;:.t..4.l Vv _1 hi ?- i..\.\.. ",lv \....•.. I ••••.. .1 ~ \AL..t.-.'lJ
labor atorv of the Louvre Xluseurn. but t \\dl still be 111 close touch \:"iLl; 'ic.m
Zafrcn-2
Calli1i and Dick Schwall. 'You can still write to me at Crocker \uclear
Laboratory, Of else the Laboratoire de Recherche des Musees de France,
Palais du Louvre. 7<;04 i Paris CEDEX0 j .
Sincerely.
Bruce R. kustn
Technical Coordinator. CH/',P
encl.
cc Richard f'\. Schwab
PIXE ANALYSIS OF THE CINCINNATI HAGGADAH
Final Report to Mr. Herbert Zafren. Director of Libraries, Hebrew Union
College.
Bruce H. Kuske. Crocker Historical and Archaeological Project, Crocker
Nuclear Laboratory, University of California at Davis.
Proton-induced x-ray emission (PIXE) analysis of the Cincinnati
Haggadah was commissioned by the Hebrew Union College in the winter of
1987, and performed by the Crocker Historical and Archaeological Project
ICHAP) at the Crocker Nuclear Laboratory of the University or California at
Davis on 13 Mav. 1987.
Introduction
The purpose of this project was 10 perform non-destructive tests of
the chemical composition of the parchment, manuscript inks and painted
illuminations in the Cincinnati Haggadah. The results of these analyses are
important to the CHAPs group of scholars, who are studying the history of
the book and early printing in Europe. As part or their research, CHAP
SCholars are building a database consisting of "chemical fingerprints" of the
papers, parchments, and inks of books, manuscripts, and historical
documents. according to era and date, region, scribal school or primer.
paper mill or parchment maker. The focus of their research has been
Gutenberg and the history of printing in western Europe.
A second reason for performing this investigation was to compare the
manuscript inks in the. Cincinnati Haggadah with the typographic ink used in . ,
the contemporaneous 42-line (Gutenberg') Bible. The CHAP database contains
the the results oj' 17<)2 analyses of ink from five 42 -Iine Bible:::.
Experimental Method
PIXE is an analvucal iechnique that uses a beam or high energv
protons to probe ihe compositionof 'the paper and inks .n a document under
examination '\ more deD.decL yet nqfl-tf',~tlnf.c(~!dp~c.r;pt!()n nl lJI.XF is given
in appendix B after an introducuon on the nature ()f x -r avs in appendix A.
The most irnpor tarn advantage of P1XE for the analysis of books and
III anuscr ipts is that the technique IS compleiety nondestructive 1t is
therefore nul. necessary to remove' even the smalles: atiquot from Uk
document heingtt~Sled In addllinl';, PIXE I~~a sensitive. m ult i-ele me ma;
method. since any element from sodium 10 the end or the periodic table can
be detected by its X -fa-y' signature if it is present in major, minor, or trace
a mounts. It is also extremely Iast, in that good sensitiviry is usually attained
in one to three minutes. And if an accelerator is available 11is relatively
inex pensive.
The need for an accelerator to produce high-energy proton beams is
the primary Iim itation or PlXE. Although we use a cyclotron a much smatter
electrostatic or van de Graaff accelerator IS adequate, The other major
limitation of PIXE is the inability to detect U1e elements llydrogen, carbon,
and oxygen. Therefore, if an ink were purely organic it woulo he 'Invisible
to the PIXE technique.
Procedures
The testing of the Cincinnati Haggaoah took place on May 1.3. 1987.
The proton beam was directed into the North Cave experimental area of CNL,
and tuned through a thin plastic window on the end or the evacuated beam
line, into the air. The final beam collimator was adjusted to provide a 2 m m
by ,3 m m beam spot on the target leaf. hence the name "proton milliprobe".
Figure 1 is a schematic diagram of the proton milliprobe
The Cincinnati Haggadah was supported hy a special lectern designed
10 hold it securely in the proper orientation for analysis yet put no more
stress on it than if it were lying open on a table. The lectern allows [or
millimeter adjustments laterally and vertically. so the desired spot on a leaf
to be tested can be positioned to exactly intercept the proton beam.
Alignment is checked with a (harmless i laser beam that can be positioned
with mirrors to be exactly co-linear with the proton beam (see figure I).
A series of thin ele mentat standard foils from silicon !./", 141 to lead
i7 L'~'~)"':''"1,i'" \"er",t. ,r~•/•~Cn~•• te-;s."te'd.\., I O.J 'c-'o.1nfLi,rm I thI'e;:. "'.Y.:·:"-rl,<-..U••l.,., l'··«,1.;d},·}·l •..,·-1'1·;.'·-·''Ur'. 1i."Lll, addl\i.r,iicl,)u.•.. '""
13th century' parchment leaf whose composition \\~e rest at the t)eglnIling ()('
ev er v. beam-in- air cv.ctotron run -w'. as measured to confirm 3 set uf values on
a materia! similar in nature to theparchment leaves in t he Cincinnati
Haggadah.
Thirty-six tests were made on the Cincinnati Haggadah. PIXE was used
to deter mine the elemental composition 01"eigi1~ parchment leaves, the black
manuscript ink on twelve leaves. the brown manuscr intink (in two leaves
and T'\1 iI1P l'OIt')I'': elf i;, '.c> f) ai n ted I'J1u mi n ')1ion I~ T hi:' ~. r \' "'1' b j.J :', "} \'.' '1 t: '111,' I" '1 ..\ Ii J. ..•••••.• 'V. \. l.' _ ..I._V\_" t- l(~ .•..l ..I'... J .~~\..- t-.'. ''.It., J ''-'<.Ail f'\- u....Li;.,.I\'v..\...~~
to strike the page for 100 seconds, and the x -r a. ~:were recor de d Data was
2
analyzed bv the computer oroeram RACEwhich provided a list of the
elements mat were Iound. If an element were nor round me program gave
the minimum detectable limit. which is a measure of the sensitivity of the
analysis.
Results
The complete results are presented in two tables and three figures.
Table I presents the results for parchment and ink, and table 2 presents the
results for the colored illuminations. The results are given two ways. One set
uables 1a and 2aJ is presented in nanograms per square centimeter, a
measure of areal density, or mass per unit area. (One nanogram is one
billionth of a gram, or 1/28,000,000,000 of an ounce.I This is as close as we
can get to 'parts-per-million", a more common unit, since we can not weigh a
leaf, or the ink on a leaf. The other way the data are presented (tables! b
and 2b) is as values normalized to the element argon. Argon x-rays come
from the air surrounding the leaf. Since the argon level of air remains
ex tremelv constant, by laking ratios to argon we eliminate some of the
variations in the experimental data due to fluctuating proton beam currents
and varying thickness of parchment from leaf to leaf. Experimental
uncertainties were on the order of 10 to 20 per cent.
The results for parchment and ink in table I have been separated to
compare the differences between them more easily. Since the proton beam
goes through the leaf, exciting x-r ays all along the way, an ink analysis is
really an analysis or ink -plus-parchment. In order to determine the
composition of the ink we must subtract out the contribution or the
parchment.
A "chemical finger prim" for parchment was determined by averaging
the elemental values for the eight leaves tested. t The standard deviation is a
~lJL-:LlCJI measure of the variation of the eiemental valuos.l Chemical
[in~erprinls fry (;lJck manuscript ink and brown m anuscr ipt ink \\'ere
(J~[ermjnec! in a similar wav These chemica! Iingerpr ints are presented
graphically in figure 2. P~ing lh~ parchment as a baseline one can ~ee the
e le me m s that ar e enhanced In the ink: -plus-p arch ment : Of pigment! -rlu~-
,,t-}(a11rc.h.... 1.1n._1f>\"1111'i • aU.nal(All.-~~" "1'".:.~.
Discussion
The parch ment cornposiiion is somewhat variable. as \\ as expected
,!! i..Ilp' ,'t, e1' t(· I h''It /'Ql' !)P ~M' .)_ L 1"" \...l •••._..:.l 41.· L. "'" 'vc..i..,! ~ ••.•.
detected by PIXE, sulfur. calcium, iron. lead and sometimes copper were
found.
The black manuscript ink composition is also variable, but contains
elevated amounts of sulfur (810';(.)' potassium. iron (630tH:.). copper (570(H~!
and zinc. This is also shown in figure 2. In mv opinion this is an iron gall ink
with copper and zinc occurring as impurities or as intentional additives, such
as drying agents, color enhancers or antiseptics. l.ead appears not 10 be a
component or the hlack manuscript ink.
The brown manuscript ink is similar to the black manuscript ink:
containing similar amounts or potassium, iron, and copper, slightly lower
amounts of sulfur, and no zinc. There may be some lead in the brown into
The colored paints are very interesting. but we are limited in what we
can say about them because PIXE cannot detect organic components of the
paint. \\ie do see the trace metals and in the Cincinnati Haggadah we can
generally determine the pigments that were used. A more complete analysis
could be done but it would require the removal of a sample.
The chemical fingerprints of some of the pigments in the illuminations
(1). leaves 33 and 51 are presented in figures 3 and 4. These figures contrast
the elements found in the pigments with the elements found in the
parchment. The following are my persona! opinions on the colored pig ment s
round in the Cincinnati Haggadah
Reds and pinks: Lead red, Pb3(}1. r; pigment or anuquitv, ii. was
probably known a~ early as lead itself Red lead occurs naturally. hut it is
usuallv made by heating litharge {PbOl to high temperatures until the
desired color is obtained.
_R.l1!~~~Azurite. or basic copper carbonate 2(=uC~C~~·{~ut.C!H~2- /"'.. m.s:
i.nportant blue pigment from U1C 1)n1 centurv uati: the midule or UK I cU-I
cent ur v It is found more frequently man ultramarine ;,luc ! lapis I,!ZUli i in
~l:cdic\~al works.
(~I'~'V' \XThl·l·eIe ad DI-,C() .Dl'(\ ('r !~I\"('(\I·r-jh:(}'P; •.. md b lack t carbon r' _- "'_, .4..1. V U. j l'~"-1l r v; ... r __ .1 L,. __ J'_., •.... \._1 _' Ut1 .• tA.\,.._ •... \.rLA. •. 1.1. ••
\'(tilt.: lead was abo a pigment of anuouiiv and one ur the most important or
a!; the lead pigments. It was the first pig mcnt to lk svntheticatlv prepare o
L)ra1-lli£~ R.p<ltgar /i.S2\;. or Orni ruent {L :nR ~ ye!lo'cl/ I. As 2SI, l.nown
..•~. -!-,l..•~'-(,-(, c•••l~.•as••s,i,'c...al ..Ii..t. im~e• _s .•.• -:-1. ~1l1,.l')()U,~')J';I1,... 'v'""•1.!....•: <.'" '::!1)if,'~_I\IL"j",..1':.I"••....,."' \..,,,),.,lf:I\I1'IU,.;,)1 \,.- \".~ ·1", \;;J.1!.1. .1-.1 I"'1'_,'(4_! J.'"-':"£IA(IU' (fl.'f{"1l,J!\,J
flrvwn: Iron oxide, Fe203. Used from prehistoric limes to the present
Gold: Gold mixed 'with white lead. Powdered gold leaf was used in
medieval times for a writing ink. It was made by amalgamating the gold
with mercury. then driving off the mercury with heat. leaving behind high-purity
gold powder.
:';"5. Many medieval manuscripts used rin sulfide (SnS2) as a substitute for
gold, since the pigment is golden in COiOL Other pigments sometimes used for
gold include lead-tin yellow (Pb2SnOq + Si02) {used 1300-17501. and Naples
yellow (Pb3(Sb04h (first synthesized in i758, although it occurs naturally
and was used since the l-ith century).
Conclusion
The parchment, inks, and colored pigments of the Cincinnati Haggadah
were analyzed with the proton mitliprobe of the Crocker Nuclear Laboratory
of the University of California, Davis, The manuscript inks were determined
to be iron gall inks, which were used almost exclusively during the l Sth
century. The inks showed no resemblance to the printing inks used in the
42-1ine Bible, attributed to Johannes Gutenberg. The colored pigments were
JUdged to be pigruerus well known 10 medieval painters anci illuminators.
Credits
The Cincinnati Haggadah was brought to Davis by H. Zafren, Director of
Libraries of Hebrew Union College. The PIXE work was performed by
member s of the CHAP group. especially R.N. Schwab, B.H. Kuske, T.A. Cahill.
and R.A. Eldred. The final report was written by BJI. Kuske. The project was
paid for hv the Hebrew Union CcHege, the LCDCommittee on Research. and
the Crocker Historical and Archaeotogical Project. through a MacArthur grant
~(}.vdr ian YCi1::(}D.
5
Ci nci nnati Haggadah
CHAPS.. 13 r-·lay1987
Table 1a.
Afr)(lUl!tS in nanograms per square centi meter.
Experi mental uncertei nties are 10 to 20%.
Parchment
Pun # leaf
7.J:..C..; 2.0 *' 40 *"
160
105
i • \ Argon ; Sulfur i Potassi urn Celci IJm §. Iron Copper Zinc lead
16 50
18 51
106
153
167 46
141 39
146 36 133
.39 .34 121 26 30 *:
45 50 133 37 80 * i
~~4~7 ~2~~~2~0~:~,~ 6~7 379
i,f1e8fJ i 147 47--r--- 124 '
\,--S_·tfl_r_lw_r_d_[)_)(:_vl_·a...:.:ti..:..o..:..fI~1 __ ...:.:3"-'0=--_-'-1.-:...:S~4 --,-I 1O~._.. 6.6
23
54
55
33
Black Ink
7.J-.7.J
~A
34
50
2
41
42
46
95
88
120
130 I
118 ,
110
109
r•.._* I~ ••• r:-u" '.. Lt:;ij!
6ro~r. ..I.n.:.t..::.:..=-----,----
-------.--------~.:-. . 49
Staruiard DeviAtion!
137
38 80 *" 36.7
84 80":, 28.6
80 *: .Ij' C' <. , .J
30.7
56.6 14.0 2.0 ..:,
40.4 26.2 i.O *:
10.0 2.0 l' 2.0 *:
47.1 5.7' 2.0 *;
20.4 2.G *' 2.0 *\
20.4 3.9 2.0*:
74.5 7.7 5.5 216
45
235
134
60
27.9 37.5 8. i 24 I 1i8
-"---=.:.2..:1....::5::.---' 8.3 . 12.-=-~ ___C7...7.:_,___'
.7.J 0./.7.J 7..Q-
~...:.:~~~u_~_n_#~Le~a~fl~A~r~g~o~fJ--~l:~~IJ~lt~·IJ~r--~,.:...:_P_r~~~t:~ca~sa~~l~~ic'~~jiru~~n~~o~§+:~lr~o~n--4:C~·~o'L~PZL~pei~~_rn_(~;~Lp~~a_~_d~
17 SO i 35 485 308 24.5' 2090 436.0 107.0 60
19 51 96 434 403 20.9 2810 845.0 2.0*: 104
22 51 124 235 170 22.8 1370 353.0 49.0' 167
25 54 154 270 208 20.0 1900 510.0 93.0 64
78 91 127: 20.6
i37
1600
4570
1620 291.0 167.0_~_215
347 24.1 1758 369.:5 861 122
~---=?-:;'-"--'-~1 :~; 1----'-----.-3-4.8------ 4.:3...::....1.1.-4'7--...,2..1...:7...4.~~..~-7-:-?..3---------4.7-~----
. Araon : Sulful:--~_P.o;;-;i-~_f!.::..._-_=f!'lciurr~_E:,~J.rlJn-- 'Cop..Eer- : zinc- ' Lt:~r:j __ :
205' 361 32.7 990' 2230 20 + 326
--=5~O,--' =2__ -,1...:.:~4:...;.1. I 8 0 __~~i'.~. __._3 4J_~. 1540 341. 0 2.0 7:~ 391)
. t1e?jfl 142 193 456 33.8' 1265 282.0 2.0 361
1H 134 1.5: 389 83.4 0.0 49
19.7
22.1
23.7
26.7
225
i c.~, I-..J{...
.340
23.1
18.9
.J -:z: L: .;.....~..-'
951
701
i 7""ZCt
i ·.J·JU
210.0 59.0
520
49.0
69.0
262.0
170
106
121
146
H34
1200
337 2G.9
50G 29.3
; -::II.U 107
345
310
32.3
366.0
4::, J .0
461.0
* Denot.:s the element \·/3S not found.
The vaiue given i~; t.he minimum detec1able limit
~: (CaUum vaiue::: fl8Ve t,2en !jiv1ded t!!j 100)
814
7
Table 1b
Ci nci nnatt Haggada h
CHAPS.. 13 1'"R11J 1987
Aroounb nor meltzed to Argon.
Expert mental uncertai nties are j 0 to 20%.
Parchment
I ! CalAr I I I ,
Run :# leaf SIAr , KIAr fe/Ar Cu/Ar \ Zn/Ar II Pb/Ar i I, .cJ '/f~;! I Cu/Pbi . i
16 50 '7C c-i 75.S: 34.61 29.01 '7 ':' i 1.9\ ':'77' 1.221 i -J-J . .J: .J• .J; ..J .!; I
18 51 55.2\ 52.3i 18.7\ 37.0! 9.2i 1.3\ 104.6: 1.49! 0.088!
24 54 27.s1 47.91 1651 24.2\ 1 cJ.,,iI 1 ·L'I..ii 62.9( 1.1SI 0.2501
·-.r. c-c C6 -n ;
,
LO _'J 27.S! .J .. I: 14.0: 7.1 t l.4j 1.4: 31.9' 3.881 0.044!
33 7_'_7.J 24.B. 91.1, zscJ. 21• 32.3; 3.9\ 1.4\ 161.0\ 0.77\ 0.0241
.39 'l-j-~'l ".:t:....L')'l 66.1; 18.31 16.91 i.-I.ii 1.71 69.4; i.26! 0.0241
45 50 27.9\ 60.2: 17.81 15.31 2.9i LSi 45.1 ! 1.821 0.0651
32.5: 184.9: 13.0; I I ,
47 2 36.3; 381 2.7\ 1os 4\ 0.89! 0.0361
C'!
. I .J. i
i
! rtean '71 79.3: 19.9i 24.8! 5.2: 161 77.21 1.56) i "_f I "-'1 , I
0:51
0.0761
iStandard Devietion 10.5: 44.8! 7.2j io.ei 4.9i 43.91 0.99: 0.080! I
Black: Ink
LJ.un :# leaf
,
S/Ar
,
KiM \ C3/Ar : Fe/Ar I Cu/Ar I Zn/Ar ; Pb/Ar j S/fe i ! Cu/Pb I
i !
! 1 ; , i I ,
17 50 560: 3~t!1'! 291 24471 511: 125: 70; 0.23! 7.267\
19 51 452\ 420, 22; 29271 880; 21 108; O.lS! 8.125;
22 t:' ! 190: 137: i
~I I 181 11051 2?_C'.J':; 40! 135f 0.17i 2.i 14;
I I
25 54 175! 135\ 13\ 1234i 331 ; 601 42i 0.14\ 7.969\
71 C'C' 1 1..,1 i ss: 261 i 101 49i 14; 0.23\ I
..J' .J.J I; ld ! 503; 1 0.0891 !
'7_IC_I 77 236: 144! 241 9981 220; 62' 1291 0.24\ 1.7071 J-J
22; 1721
;
~., 77 173; 138: 797: 59; j??; 0.22\ 1 .41 11 .~I I .,.;.J ~~.
41 .34 283: 1 :,;) 20: 1 108: 'IUc: 41: 1 4'7' P'IFi r- lC'7!
-'-; I .J~ .J i ~. _'.L J: !.. ·_I.Ji
A--; ~ .i• 2r::q~ 142: 2i 1231 ! 332; t:"71 0;= 0.21 : 4.066; '"1"'::'" .J...,. .J.J' JJ",,'
46 50 424; i0171 'cI:e_)_'l 7.J877.J\, 391 222: 1 161 0.1 'I:i 3.3651
48 ? 314' 740: 1473! 2651 152' 0.21 !
i
'- , , 29; 195: 1.353~ I ,
, t'1t'3f1 , 290.0~ 319. L 22.7t 1608.8: 336.4; 78.6: 1 14.0: 0.20; 3.61
:Standard Deviation , 138.9i , 300.6; 4.8; 103Q.9: ~?_20 ~?' _6_2 .f,o.~I. 405; c' '? 9' O.O.J; ~
nrevn Ink
Run #: Leaf
49 2
~;/Ar
150
KiAr C<liAr
176; 23.9:
306; 23,7:
Fe/Ar
122
723
1048
ClJiAr ' Zn/Ar PblA:- 3/Fe , Cu/Pb i
6:::.4,
861 :
,'1eflrt
;~;tan,i<1rct Deviation
50 ?'-
163:
.?:..."_"_ZI.:.?.,.
23Fi.
~' u 269" 1 r ..,.
I. (
i36.0'
19.2,
240.8i 23.0'
915: o.i.
885.1
229.8
197A
48.9'
0.0 a.o;
77.3i
~_..........::..6.:-.4_..~:.~:.1. 2.5
i6.2
Table 2 a
(loci nnett Hagqaoatl
CHAP;:,-' 13 t'lay 1987
Aro(lunb in !1dflogrd!l\3per square ctilti meter.
Expert mental uncertei nties are 1(\ to 20%.
lRun #-==~~..=~=-AI_rqslr.!i]~!!!j}~.LFu\.r;ti1~Tsst~' ~I~~~IJ!ir.-;c(l~t=.-u;~ff;~_-._~Jad J __. O_~het=- !
I 1eat c: ' ; ;' , , , ' " ,
;, ·U ~ --.' ! -+-- I , ~ __ --+- _. .L -.-.\- ~,__ .•~ :
; 18 (parchment) 153! 84.4i 8u *: 28.6\ 56.6; 1<1: 2 *: 160:
;20 (blue) 42.4; 7.6: 80 *: 9.73; 81.2l 9356: ") *' 257:
'21 (pink) 97.3; 283; eo *' 30.5' 63.5; 27.2 2 *' 432
.z--s {,·t·~~;o·\., -:=:;-=R=-.-7=r.-. 't-=.S-':.!,. 17--::; •·. t·"!).·.·1"-r.o\): --~;:'.·:1~'/~; ~::~·t'-f------=?-1*, ;:-7::-G.-.:0+,..----.
leaf 54 ......J ..__ • J_ •• _. ~. ~' -+-
\24 (parchment) 1671 6.4; 80 *i 27.5' 40.4; 26.2: 2 *, 105,
_'!.-'?'.:'..•{.•~'~. old) 4·'.:'.,.;.. oPH~.!.',_·.: 0°0·1 *. ;i :_'..'.':, '•:1.".L•,O! ",7::I••o• .-t,"' r~.,' i ·L-'U,-_''jU"'''(•).\.i.• li,~\".l,d l-'•L•~u~i . . .---t"---.--------t--.----.~0--" ---7--- ----;---------j--.-----,---'--------'---
, leaf 3~ I ' : " • !33 (parehlnent) -'--··1461-- 36.2~ 133! 38~·~4·T- 1f--s. 7~---2*: 23-51--------:
!34 (blue) 40.6; 25.2( 80 *1 i 1.81 4921 9220; 2 *l 963;
:36 (brown) ;:;4.6: 4371 2441 29.9: 18031 133 7021 350'
! 38 (qreu) 124i 1802, 80 *i 3.7i 36.9\ 4. i, 2 *; 33000, ;---·---I~.f ~.,~ ------- ----r--"-- ----r-------c·_-----t-----·---;
. !e,~, _'""t • ,: : , , . ., ,
;39 fparc-hment)----121l·-2S·:7r---- 8(f*T---i2~T-·-XO~4r-----·-·-·-----2 *7 84}f----·------~·
;40 -<gold) 6.8-.2~, ---8-1-9-, .-.----80--*-,-.----c-.-t,----1-40-.---1-7.8.5.;,..--2-4-8-;--19-7-0-(1~. --G--o-ld-2-3-1_(I. 1eaf s ~ !! ! I i ~ !
t I· '- ~ ---+._~~ -!-- i -i-----.l..--- .:.. ~.---_--_--' !43 (parchment) 190: 53, 80*1 33.7\ 30.9i 4 *, 2 -i'. 1131
;44l"+·~1·n\ 11··; ~5C;: C;u'l; 19~ QA··' sot .')* 14.91, ! '\.::iU1 .•- : ~ • br _ __; _: dl l,.l~_bj -il",; ~_. u:-'-- _ :---. lea1i----. ---···-------·-··----------·----r---- -.--.-----.
,51_~~~j~)·=_~:,~_i.L?L1iQJ =.._. .~.~~9J_._. JJiL_~l~lL.._:)6ci~ 19~ 1Q*1~~~~-i~c9·5·00,
* Denotes the element was not found.
he vel ue given ie the mi ni mum detectable Ii mit
:3 Calcium val
Folder 7: Cahill, T.A., B.H. Kusko, R.A. Eldred, and R.N. Schwab. Gutenberg’s Inks and Papers: Non-Destructive Compositional Analyses by Proton Milliprobe, 1983-1984
No full textAll of the items in this folder are related to a published article: Cahill, T. A., B. H. Kusko, R. A. Eldred, and R. N. Schwab. "Gutenberg's Inks and Papers: Non-Destructive Compositional Analyses by Proton Milliprobe." _Archaeometry_ 26.1 (1984): 3-14. Two of the items are offprints of this article while three items are photocopies of the offprint. Three of the items are typewritten manuscript versions of the article while another item is a typewritten manuscript of only a portion of the article. The remaining items are correspondence between the authors and the staff of the _Archaeometry_ journal, and related materials, regarding the publication of the article. Non of the offprints have been digitized and are not represented here.The items in this folder are part of the Thomas A. Cahill Papers--Crocker Historical and Archaeological Project, 1981-2009. They are from Series 1: Thomas A. Cahill Research Papers, 1981-1994. This series consists of various research papers and published articles based upon Dr. Cahill's research using Particle Induced X-ray Emission (PIXE) techniques in analyzing inks and papers
Folder 33: Kusko, B.H. The Potential of Particle Induced X-Ray Emission for the Study and Conservation of Books, Manuscripts and Historical Documents, 1988
No full textThis file contains an abstract and typewritten manuscript of a paper presented at a conference: Kusko, B. H. "The Potential of Particle Induced X-Ray Emission for the Study and Conservation of Books, Manuscripts and Historical Documents." Presented at the Conference on Technological Advances in Conservation and Geoarchaeology, Santa Barbara, California, June 12-14, 1988.The items in this folder are part of the Thomas A. Cahill Papers--Crocker Historical and Archaeological Project, 1981-2009. They are from Series 1: Thomas A. Cahill Research Papers, 1981-1994. This series consists of various research papers and published articles based upon Dr. Cahill's research using Particle Induced X-ray Emission (PIXE) techniques in analyzing inks and papers.. ", .. \
\
I!
\
\,
ABSTRACT FORM
TECHNOLOGICAL ADVANCES IN CONSERVATION SCIENCE AND GEOARCHAEOLOGY
JUNE 12-14, 1988 UNIVERSITY OF CALIFORNIA SANTA BARBARA
PLEASE TYPE YOUR ABSTRACT IN THE SPACE BELOW --------- DEADLINE MAY 1
-------------------------------• --------------------------------------
Jhe Potential of Particle In<.1ucedX-Ray Emission for the SJudy and
Conservation of Books, Manuscripts, and Historical Documents
Bruce H. Kusko
Crocker Historical and Archaeological Project
University of California / Crocker Nuclear Laboratory
Davis, CA 95616
The Crocker Historical and Archaeological Project (CHAP) at the Crocker
Nuclear Laboratory of the University of California at Davis has been using
Particle Induced X-Ray Emission (PIXE) for the' arialyst's' of thepaper.
parchment, and inks of books, manuscripts, and historical documents. PIXE is i _ a non-destructive method capable of determining the elements from sodium
(Na, Z= 11) through uranium (U, Z=92) that are present in major, minor. or
trace amounts. The primary focus of CHAP has been historical: we have been
using PIXE data to answer certain long standing questions about the
development or printing in western Europe in the l Sth century. PIXE data
can also be useful in conservation and restaura~ion··8tuEiie3;·in:·wl1ich·the first
step is to understand the physical and chemical properties of the papers,
parchments, and inks of the document in question. For example, chlorine
bleaching, alum sizing, and mineral fillers or colorants can be detected easily,
and the composition of the ink can be studied if it is not purely organic. This
paper will describe the capabilities of PIXE and explore its potential in the
field of document conservation:
--------------------------------------------------------------------
ARE YOU INTERESTED IN LEADING A WORKSHOP SESSION? YES NO >(
~o c;>~ 7 tAo.l-\ J ~c..v--, r:' f\'z; k.,f oJ" \ Doc.'-'v '" (I-J->"
I . C-- '1/' ~lA\G A V +'5
SEND THIS COMPLETED FORM TO: DR. STANLEY V. MARGOLIS
MARINE SCIENCE INSTITUTE
UNIVERSITY OF CALIFORNIA, SANTA BARBARA
SANTA BARBARA, CA. 93106
TOPIC OF INTEREST
TELEPHONE # (805) 961-4496
The Potential of Particle Induced X-Ray Emission for Ule Study and
Conservation of Books, Manuscripts, and Historical Documents
Bruce H. Kuske
Crocker Historical and Archaeological Project
Crocker Nuclear Laboratory
University of California
Davis, CA956 16
The Crocker Historical and Archaeological Project (CHAP)at the Crocker
Nuclear Laboratory of the University of California at Davis has been using
Particle Induced X-Ray Emission (PIXE)for the analysis of the paper,
parchment, and inks of books, manuscripts, and historical documents. PIXEis
a non -destructive method capable of determining the elements from sodium
(Na, 2= 11) through uranium (U,2=(2) that are present in major, minor} or
trace amounts. The primary focus of CHAPhas been historical; we have been
using PIXEdata to answer certain long standing questions about the
development of printing in western Europe in the 15th century. PIXEdata
can also be useful in conservation and restoration studies, in which the first
step is to understand the physical and chemical properties of the papers,
parchments, and inks of the document in question. For example} chlorine
bleaching, alum sizing, and mineral fillers or pigments can be detect~d easily}
and the composition of the ink can be studied if it is not purely organic. This
paper Willdescribe the capabilities of PIXEand explore its potential in the
field of document conservation.
I. Introduction
I would like to thank Stan Margolis and Luis Monreal for inviting me
to to speak at this conference. I am an atomic physicist and relatively new to
the field of conservation, but for the last ten years I have been involved in
the cyclotron analysis of books and manuscripts through the Crocker
Historical and Archaeological Project, or CHAPfor short. CHAPconsists of a
group of scholars in the sciences and humanities who are engaged in
Potential of PIXE... B.Kusko 2
historical, art-historical, bibliographical, archaeological and other related
research programs which employ the facilities of the Crocker Nuclear
Laboratory (CNL).The instrument we use to study books and manuscripts is
called a proton milliprobe, which is based on a technique known as Particle
Cvj\,\\tl.... S WIll ~es v,,,,e ,...1 ?J-+ j)
Induced X-Ray Emission, or PIXE1\Ourfocus has been the~ history of the
book. The largest effort has gone into our study of Gutenberg and the
incunabula period, when printing with movable metal type was invented
and spread throughout Europe (1450-1500). 1 _' :/0
~~;t4
As the technical coordinator of the CHAPsprogram I affiAconfidentof rf fl\A-1.. ~
~ '(' e'S00V\$\01€ the numbers+ obtain. But as e.,~. 1r1>.r" J)'"A .{(.,o. -.((.0...rr;;.c'-l ofov-r ~;,J~A10_ ••• :~.J..0. p-€"w~ evt-fovl ~S(-\tTs. ~ 't
a scientist collaborating with humanist scholars, I often find myself ignorant
of the details of the historical or bibliographical side of an issue. I sometimes ,
feel that I have answers, but that I don't know what the questions are. I will
tell you a briefly about CHAPsand the technique called PIXE,with the hope
t .iJ;l (that conservators of documents will see a use for the information provided
~ byPIXE. \
--\ rt---- ~--.....-./0 C.
Utilization of the CNLcyclotron to the study of books, manuscripts, and
historical documents grew out of fortuitous circumstances that brought
i together two very different research projects that were being pursued on
\ the Davis campus.
The one has to do with the cyclotron analysis of smog (figure 1).
Essentially, air pollution is collected by pulling air through clean filters and
its elemental composition is determined by PIXE.Physics professor Tom
FL
Potential of PIXE... B.Kusko 3
cahill and colleagues use the (PIXE)results to help pinpoint the sources of
the air pollution; whether it comes from man -made sources like automobiles
and power plants, or natural sources like forest fires and volcanos.
The second project is history professor Dick Schwab's investigations Of. r-2\t
the great 16th century Encyd{~jje of Diderot (figure 2). Diderot's covrt-vuvel!'5%\ t
Encycjope.:iie.,printed over a period of 20 years, contained 35 volumes, t=- s R
including 11 volumes of magnificent engraved plates. It was so highly
admired and sought after that almost immediately, counterfeits were being
~
made. Schwab's researches, based on careful visual examination of over 100
folio sets, resulted in a seven-volume Iaveatory t>f the En{yd{~ilewhich
was designed, in part, to establish the original text out of the many
counterfeits, cancels, censored pages and confusion of variant editions.
As Schwab and Cahill became a-ware of the problems with which each
was dealing in their widely differing fields, they became persuaded that the
PIXE technique that worked so well on aerosol filters might be effectively
),-/D:J applied to problems of physical bibliography and the history of the book.
After all, to the cyclotron, the ink on a page of a book is almost identica1-te ~
'7Ts-r
smog collected on a clean filter.
2 _Proton Induced I -ray Emission
Figure 4 shows the essential features of PIXE.A beam of high energy f~L
protons generated by the cyclotron passes through the page I exciting the ink
and paper being analyzed into emitting characteristic x-rays. By
Potential of PIXE... B.Kusko 4
characteristic I mean that these x-rays contain information about the atoms
in the object being analyzed. The energy and intensity of the x-rays are used
to determine what elements are present in the ink and paper, and in what
amounts.
There are a great many advantages to using PIXE.(Table ) Most
important for the analysis of books and manuscripts, the technique can be
made completely non -destructive, so that one cannot determine, even with
careful examination, that any analysis had been performed. It is therefore
not necessary to remove even the smallest aliquot from the document being
tested. Furthermore, PIXEis a multi -elemental method, since any element
from sodium through to the end of the periodic table can be detected (by its
x-ray signature) if it is present in major, minor, or trace amounts. It is a very
sensitive method, with the capability to detect elements present in amounts
down to lO- 13 to 10-14 grams. {It is quantitative in an absolute sense,
needing no standards for calibration purposes, only the parameters of the
experimental setup} It is extremely fast, in that good sensitivity is usually
attained in 60 to 180 seconds. And if an accelerator is available, it is
relatively inexpensive.
This need for an accelerator to produce high -energy proton beams is
the primary limitation of PIXE.The other major limitation is the inability to
detect the elements hydrogen, carbon, and oxygen. Therefore, if an ink were
purely organic it would be "invisible" to the PIXEtechnique. Also, as with
any x-ray method, we see elements and not compounds.
3- The Davis Proton Milliprobe
IJ-0( Qt
At Davis we do PIXEwith what we call the proton milliprobe.
The Davis proton mi11iprobeis located at the Crocker Nuclear Laboratory of
the University of California at Davis (figure 5) At the heart of the
laboratory is a 300 ton cyclotron (figure 6). the one used a Berkeley for
many years before it was "retired" to the Davis campus is 1965. The
cyclotron provides the high energy proton beams that are used to probe the
o 1A}-\1~ \-1-R
composition of paper and ink. 'lll:is is the control room of the cyclotron
(figure 7). Although it is quite complicated, once the beam is tuned up it
takes very little effort to keep it going. ~ ~-( -r-'\'Jt..,-\- ~l5--Y1J e _
CovV\1-Vv-9 vI~ e
The proton milliprobe is at the end of the target beam line and is
'8
shown here schematically (figure 101. The proton beam passes out of the
evacuated beam line through a thin plastic window, and reaches the target
page after traveling through about one inch of air. It then passes through the
page, exciting x-rays, and is collected and counted in what is known as a
Faraday Cup. The x-rays emitted from the page are detected with a detector
just below the beam line. i, ~+ed. +0 0 e l:i-d ~~V\ 0 _'?> c-, '" ~ '3, 0 'W\ '-"'1 -'
\tIe~\<Aw\~~\[ *fl1e. /oQ~",,", c (AV1 \,~ t?\. j 0 (CAlI\taQ.V\~e... "'L1r, .Vl
I-- 1.\ \ -t -+~ A CO\I"lQCA-r'VJ'-1 7V\-€. T0.1~+S O\.V"'€. O\.\l~V\e~ j-Ia CA. (}.:se~ ~Qro ~ 1\
~~+cV\ la-e~fI""\ I by --t'1e. UJe of' VV\\'4'vo-r::' '
Because of the low beam currents used, the energy lost in the target
page is always quite small. Typically, the energy deposited is equivalent to
that provided by a 100 Watt light bulb at a distance of 50 em, and much less
Potential of PIXE... B. Kuske
than sunlight or the energy deposited by a photocopy machine. Nevertheless
we performed extensive tests to assure ourselves that the proton beam is
completely harmless to papers and parchments. The actual process of
analysis is so safe that it is possible for us to stand directly next to the book
5
Potential of PIXE... B.Kusko
so that we can supervise the safe handling of it. As a matter of policy we
require the curator or other representative to be present at all times during
the testing of their book. [+- \J J--;(
6
LrIt?
F \ I
For the testing of large bound books aBe oti'ieI balky w(}rks, we
needed to design a special lectern so that the individuat pages could be
positioned quickly, accurately, and safely on the target plate (figures 11
and 12). We consulted with rare book conservators and designed it so that
it can hold the volume securely, make it possible to position a single leaf of a
bound volume in position (at 45 degrees) on the target plate, but in no way
put a strain on the binding or pages they would not get from normal reading.
When hanging sideways, the weight of the volume is distributed along the
bottom and side edges. The device is designed so that there can be precise
adjustments of the book up or down or laterally in relation to the target
plate and proton beam coming through it. /( ~ r) '"")
~e l'7CtAV>'\ ',5 t'"- "",oJ4 s-; L-0: \.1 '1CI..(
L
.
Th~~figuret (figures 13 a ) ~ representative of the x-ray ::f I'"LR
spectrum acquired with the proton miniprote, and are taken from one of out:
\t ~O1;.l5 -+\-\e ~~~{ (.\£15 Ie. . S eW\ rII.(d
early G tenberg analyses. ~u is the x-ray spectrum-of pape .and on ~ e e \~ •
the ig:htis4~ay spectrum of black ink. Since the beam goes through the
page, when we analyze ink we get x-rays from the ink and also x-rays from
the paper. We have found paper to be relatively homogeneous chemically, so
by subtracting its contribution to the paper -plus-ink spectrum, we can
arrive at the elemental composition of the ink. (Unable to get absolute
numbers for ink atone.)
Potential of PIXE... B.Kusko
These x-ray spectra are analyzed by computer. Quantitative results
are available for all elements (above sodium) 30 seconds after the
completion of data acquisition. This immediate access to results allows the
intelligent modification of protocol if something unexpected turns up.
4. Applications of the PIXETechnique
An early example of the sensitivity of the PIXEmethod is shown here
(figure 15). We analyzed 33 consecutive pages of an 18th century travel
book by Savary (let/res sur lEgypt~1786), and plotted the results. It was
puzzling to the scientists in the group that the elemental values were
consistent for eight pages, then jumped to a different value for eight pages,
and so on. Of course Dick Schwab immediately recognized that we were
seeing signatures, (figure ) and differences in composition from one large
sheet of paper to another.
These results encouraged us to pursue the PIXEmethod for the testing
of the papers and inks of books and manuscripts. The information we have
obtained has made it possible to make new contributions to the discipline of
descriptive or physical bibliography. We have been able, for instance, to peer
into the day-to-day workings of Gutenberg's printing shop. While these data
tJ~~vV)
o v..,te
V
7
Potential of PIXE... B.Kusko 8
are interesting they are not relevant to this symposium. The point is that the
proton milliprobe is a tool that can be exploited for conservation studies.
OUrexperience in this field has been limited. I will describe our part
bt'
in a large study tf0nducted by Timothy Barrett, now the director of the
Papermaking Facility of the University of Iowa). Barrett had collected 126
leaves of book-paper manufactured between 1400 and 1800,62 of which
were in good condition, and 64 of which were in poor condition. One of his
aims was to determine why some paper remained in good condition while
others deteriorated badly. His measurements included tests of pH, fiber
length, gelatin content, and ultrasound properties.
Our job was to measure the sulfur, c torine, and residual metal l,. \~'>lO ~DY'V\e
ov« fv~\ n$v\+S w~~ Joo~ bQ ~1o\\5"'€c!a,:r ''''Vl VI'71 ~r o.r\.{
content of the papers" In general we found that the good paper had higher. ~-..re\~'~vW.+lO().,
~~
calcium levels, while the poor paper had higher sulfur, aIId potassium, levels .
.air pal19tien A \uvv) Y- Af- 50t1) )se~ ? I~ I~~ \ V) ~ e
I -,\ .
~V\~-e.'vv\IA\.(~~ ~(e.eJS Mo...\£e"'J ~~ ~e;..~e"o...C\O cc
k\c c;,.. ~ ���•.•+--te-r- <,
atWll~ b~~, \1I'\\-e(/\+lool'-g.l(y IOlr 0c-c~~ev\+1i LV\t~'vc41
Pages were seen with very high chlorine levels, which probably means
the page was washed or bleached at some time. (Clin papermaking only
after 1774.)
;;; I f2vf'v-\ fa,x.e 1 5J 0~ S vJ e f? ~ VIC-.. \,Y~~ - --::J (2 5 (' c:' 0C
S>vV)G \ I \ov\)vVVI\S~ ~ y.Q U()~\sL." '7e v-}5 -f-hct1 J\5 cot Dv ~ ~
\j'Je", ~V""\ 0 \~ G~ re'-f., \~ey ~~ ")~o vJ L.,+ ~ ~Q c:::..J€ vv\l CIjX1 5~ floc
VVl'otLs. ~~ c-.l-:-o ~ ~7~L_<A\ VV\-e-h·Js +h<A+- c-,c+ CAS cuJ~/1 '2RV3
-+0 o"f~6~~'vV)-
WQ. {ovv'"/1 G o~ f~ II ~ox.e ~ S~o+5 \.Ne.~ v--.v
~~f·\Oll\_t fY\)~ [\.-e J J rfOV---~\~) C ~-e~~ ~ -fCv- \!-,ye.e s()Z~ f ~
r:0 V\ ~ \v-t-e ~ v..v'\. 0 r: ~ ~..J 0-t II"\A fA 0V'I \-:) u ~ ~ VV\ ~ IV'0Y'\) ,0.-", t.. 0 V) a,
C7~"Qt ('v~\~-e~ 2...0 -t\VV\e5 VVC0~ ~v- ~~'v\ f1-o sVVJ'<;)vV'\~C~ (""'F-ev ~
l+ \~ (\ev.-v VV\O--re vv~,,\<- Y\~~5 ~ 012. ~()""«' OV'-{;XI'V\-) I L::,Q-}h. vvd'--.
?\~& c- I-,~ 0 f",",-J" vv"-€ j.~1. ~;s.
r>.Kusko
"---- -
Cl--~88!!t'6!\f!leallll "iI'[f9S. We stuoieo three leaves that
were high in sulfur in more detail. We scanned the top, outer and bottom
margins as shown in figure .The results for sulfur, potassium, calcium, iron
and zinc are sho-wnin figure . It appears that sulfur can enter a book
through airborne sources, probably as sulfur dioxide gas and sulfate
_-"p,--~rtic1es.7
( ~------- ..--
/
I
I
Potential of PIXE... B.Kusko 10
6. Conclusion
I have tried to show that the proton rnilliprobe is a tool that has a
wide range of potential applications. PIXEcan be applied to parchment,
papyrus, and other writing surfaces, as well as art forms that use ink,
crayon, paint and other writing media.IOf course, to be most effective, data
provided by the proton mittiprobe should be used in conjunction with other
{more traditional} methods of the study of documents. A broader knowledge
of the chemical and physical properties of ink and paper will assist the
custodian in evaluating good storage conditions and restoration procedures ~
-----___ ~f~o~r~boo~k:s~a~n~d~m~a~nu~oc~n~·p~ts~. --------------------~------- "'\ \ \ \' l . v-e ~\.-eeo r ~'5I'OV\ \~y~\f'5 O\{ 01'~Q...r ~o-t-eVl /(r, ~~ \ <..CA.ft()V'\S o.
~
I' e' -I' -'I\U.«;h1 (-e~~"",",\...[ '5~YlG- tA~~o--J.'5 .
0\.l"'1~ o-: 0 V\ "V\ J1?'- '" J 6. Acknowledgements
This work has been almost entirely supported by a MacArthur
Foundation award to Adrian Wilson. Additional funding has come from the
University of California, Davis
Folder 39: Kusko, B.H. The Development of Particle Induced X-Ray Emission for the Study and Analysis of Museum Objects, 1989
No full textThis folder contains two copies of a typewritten report: Kusko, Bruce H. "The Development of Particle Induced X-Ray Emission for the Study and Analysis of Museum Objects." Progress Report to J. Ligot, Director, LRMF. Only one copy has been digitized and is presented here.The items in this folder are part of the Thomas A. Cahill Papers--Crocker Historical and Archaeological Project, 1981-2009. They are from Series 1: Thomas A. Cahill Research Papers, 1981-1994. This series consists of various research papers and published articles based upon Dr. Cahill's research using Particle Induced X-ray Emission (PIXE) techniques in analyzing inks and papers.PROGRESS REPORT:
The Development of
Particle Induced X-ray Emission
for the
Study and Analysis of Museum Objects
Submitted by: Bruce H. Kusko
Fulbright Research Scholar
AGLAE
Laboratoire de Recherche
des Musees de France
to: M. Ligot
Directeur, LRMF
28 February, 1989
RESUME
Le Louvre est le premier musee au monde a posseder un
acceIerateur de particules pour l'etude et l'analyse des oeuvres
d'art et d'archeoLoqi.e. Le Laboratoire de Recherche des Musees de
France s'est donc equipe d'un outil t res puissant qui offrira aux
scientifiques de musee la palette des techniques d'analyse par
faisceaux d'ions acceleres qui comprend PIXE, PIGME, NRA, RBS et plus
tard datation C14.
Le rapport d'avancement consigne les travaux que j'ai accomplis
entre le 15 septembre et le 28 f'evr i.er 1989. Pendant cette peri ode
nous avons commence par monter un systeme PIXE d'analyse des oeuvres
d'art des collections de musee. PIXE est une technique multi-elementai
re, sensible, bon marche, rapide et ce qui est le plus
important dans le cas d'espece non destructive. Nous avons ainsi
obtenu des resultats preliminaires sur des echantillons de verre, des
etaIons qeoLoqi.ques , des pigments de peinture et des objets en or.
D'une certaine mani.ere, ces experiences ont ete plut6t un
apprentissage pour moi et l'equipe AGLAE. Nous nous sommes
familiarises avec l'accelerateur, la chambre d'analyse, le detecteur
de rayons X, l'eIectron.ique d'acquisition. Les premiers resul.t ats
sent; t res encourageants, il reste pourtant beaucoup de travail a
fournir pour que le systeme PIXE d'AGLAE soit operationnel en
routine.
Nous n'avons, de plus, qu'un temps limite de faisceau pour le
PIXE, puisque la priorite est donnee aux tests -verifier que
l'accelerateur est bien conforme aux specifications du constructeur.
L'accelerateur presente quelques problemes avec la source d'ions avec
comme consequence un courant de faisceau Leqeremerrt instable. De
plus, nous avons utilise une chambre provisoire. La nouvelle chambre
definitive a ete construite a Strasbourg et est en cours
d'installation. Il n'y a pas a l'heure actuelle un moyen sur pour
mesurer le courant de particules dans le cas d'echanti Ll.oris epai.s,
c'est pourquoi les resultats presentes ici ne s~nt que relatifs. Un
hacheur de faisceau (un composant pour mesurer le courant en
prelevant peri.odq.uiement; une partie du faisceau) est en cours de
construction a Jussieu-Universite Paris VII et sera monte au Louvre
en avril.
Nous avons porte nos efforts particulierement sur 'quatre
etalons de verre, qui represent erit les d.i f ferent s types de verre
etud.ies par les archeo Loques et les historiens d 'art. Ces etal.ons
sont bien connus et contiennent 27 elements chimiques entre le sodium
et le plomb dans des quarit i.tes variables comprises entre 100ppm et
35%. On a obtenus des resu l.tats avec une erreur relative comprise
entre 10 et 20% ,avec parfois des desaccords d'un facteur trois.
Les premiers echant i l.Lons que nous avons ree.l Lemerit analyses
sont des pigments de pe inture broyes provenant de la boutique "A la
momie", une maison de commerce en exercice pendant les 18 et 1gemes
siecles. Nous avons alors prouve que PIXE pouvait etre utilise pour
determiner les elements majeurs, mineurs et traces rent rant dans la
composition de ces pigments. De subtiles differences ont ete decelees
entre des pigments de meme denomination, et au contraire des pigments
avec des noms differents ont la meme composition chimique.
Le systeme de faisceau extrait a ete teste sur plusieurs
objets, y compris sur un tableau-faux primitif italien- , un cadre
dore du 15eme siecle et une petite statue en or antique. Pour
l'analyse de la plupart des objets de musee nous serons amene s a
utiliser ce systeme a l'air. 11 est donc crucial que ce systeme soit
parfaitement regle.
On a egalement commence a etudier l'atmosphere a l'interieur du
Louvre afin de determiner si des poussieres presentes dans les
galeries s~nt nocives pour les oeuvres d'art qui y sont conservees.
L'analyse des filtres aerosols pourra etre effectuee par AGLAE avec
seulement des modifications mineures sur le porte-cible.
Les resultats presentes ici ne s~nt pas entierement
satisfaisants. 11 est tout a fait rassurant que tous les equipements
et composants fonctionnent bien pour acquerir les spectres. Mais je
pense qu'il faut encore reduire les erreurs experimentales en
ameliorant le traitement des spectres(materiel et logiciel) pour que
le Louvre soit dote d'un systeme PIXE sur et precis.
EXECUTIVE SUMMARY
The Louvre Museum is the first museum in the world to have its own
particle accelerator for the study and analysis of works of art and
archaeology. The Laboratoire de Recherche des Musees de France has
thus taken a bold leap into the future with AGLAE, a powerful "high-tech"
approach to the conservation of our cultural heritage.
This accelerator will enable the museum scientists to use a variety
of ion-beam techniques on works of art and archaeology, including
PIXE, PIGE, NRA, RBS and C-14 dating.
o
This progress report describes the work I accomplished between 15
September 1988 and 28 February 1989. During this time we have begun
to set up a PIXE system for the analysis of works of art in the
museum's collection. PIXE is multi-elemental, sensitive, inexpensive,
rapid, and most importantly, non-destructive. We have so far
acquired preliminary data on samples of glass, geological standards,
painting pigments, and gold artifacts. In a sense, these experiments
have been more of a learning experience for me and the AGLAE team. We
are becoming familiar with the accelerator, the target chamber, the
x-ray detector, the fast-pulse electronics, and the x-ray spectrum
reduction code. Although we have made a good start, much work still
needs to be done to make the AGLAE PIXE system "state-of-the-art".
We have had limited access to beam time for PIXE. Of course the
highest priority has been to ensure that the accelerator meets the
manufacturers specifications. The accelerator has had problems with
the ion source; as a result the beam current has not been very
stable. The target chamber we are using is a temporary one. A new one
has been built in Strasbourg and will be installed in March. There is
presently no reliable way of measuring the incident beam current for
thick samples, thus all the results presented here are relative. A
beam-chopper (a device for measuring the beam current) is being built
at Jussieu and will brought to the Louvre in April.
We have concentrated our efforts on four glass standards, which were
designed to duplicate the types of glass studied by archaeologists
and historians. These standards are well characterized and contain 27
elements between Na and Pb in quantities from 100 ppm to 35%. We have
been able to obtain results that are generally within 10 - 20% of the
given values, however, some occasionally there is a discrepancy of a
factor of three.
The firt "real" samples we have analyzed were pure pigments from the
boutique "A la Momie", a house of commerce in Paris during the 18th
and 19th centuries. We have seen how PIXE can be used to
quantitatively determine the major, minor, and trace elemental
composition of these paint pigments. Subtle differences were detected
between similar pigments, and pigments with different labels were
shown to have the same chemical composition.
The beam-in-air system has been tested on several samples, including
a false italian primitive, a gilded frame from the 15th century, and
a small gold statue from antiquity. For the analysis of most museum
objects we will be using this extracted beam system. It is thus vital
that we get it working well.
We are about start running air sampling equipment inside the Louvre
Museum in order to determine if any harmful pollutants are present in
the galleries that hold precious works of art. Analysis of the
aerosol filters can be done at AGLAE with only minor modifications of
the target holder.
I must say that I do not feel very confident about the numbers
presented here. I am glad we have all the equipment working to the
point that we can get results, but I have doubts that all the
hardware and software is working properly. We must now work to find
and reduce the experimental uncertainties, in order for the Louvre to
have a reliable and accurate PIXE system.
Progress Report, Fulbright Grant, 15 September 1988 - 28 February 1989
Bruce H. Kusko
AGLAE - LRMF
I. INTRODUCTION
During the last four years the Louvre Museum has been undergoing
a major renovation. Not only is the main entrance going to be a giant
glass pyramid, but three stories under the pyramid a team of
scientists will be bombarding precious works of art with a particle
accelerator. Analyse au Grand Louvre par Accelerateur Electrostatique
(AGLAE) is a part of the Laboratoire de Recherche des Musees de France
(LRMF), which has been given more space and equipment in a new
underground laboratory. It is only recently that methods of analysis
using high energy ion-beams (protons, alphas, 15N, etc) have been
applied to works of art and archaeology, and usually by physicists
working in nuclear laboratories in their spare time. The Louvre Museum
is thus the first museum to have an accelerator to be used exclusively
for the study and analysis of works of art and archaeology. The LRMF
has taken a bold leap into the future with this powerful "high-tech"
approach to the conservation of our cultural heritage.
II. PIXE at AGLAE
My expertise is with particle induced x-ray emission (PIXE) and
I have been concerned with developing a PIXE system at AGLAE for the
study and analysis of works of art. We have had several opportunities
to do some PIXE analyses under vacuum, including pigment samples,
glass standards, geological standards, and gold samples. Although the
spectra were acquired under conditions that were not ideal, we were
able to perform tests of the target chamber, x-ray detector and
electronics, and the PIXE spectrum reduction code. All results
presented here are therefore considered preliminary and subject to
change.
a. Accelerator
The accelerator, a 2.0 Mev tandem pelletron, was purchased from
National Electrostatic Corporation in Middleton Wisconsin. It is
capable of accelerating protons from 0.3 to 4.0 Mev, alpha particles
from 0.3 to 6.0 Mev, and 15N ions to 8.0 Mev. In addition it can
accelerate deuterons and 3He ions. Guaranteed beam current for protons
is 5 pa through a 1 mm2 collimator. It was installed in the winter and
spring of 1988, and the first beam was realized in June 1988. Tests
and practice with the machine have been taking place ever since then,
and are expected to continue through the end of March.
B. Target area
The target chamber we are using is a temporary one. The target
ladder can hold up to six samples and is moved manually. The sample
surface is perpendicular to the axis of the incident beam. X-rays are
detected at a backward angle of 135 degrees. The detector is
collimated, and subtends a solid angle of 0.5 sr. A new target chamber
has been fabricated in Strasbourg and will be delivered to the Louvre
on 3 March. This new chamber is very versatile and will be used for
PIXE, PIGE, RBS, and NRA.
A beam-chopper for measuring the incident beam current has been
built at Jussieu. It is presently undergoing tests and will be brought
to the Louvre at the end of March. Presently the beam current is
determined by measuring the charge acquired by the target, target
holder, and target chamber, which are electrically isolated from the
rest of the accelerator. Since this method is not reliable, I have
designed and will be building a device to determine the beam current
by measuring the protons backscattered from a thin mylar foil placed
in front of the target. This thin foil monitoring technique has the
advantages of eliminating charge buildup on insulating samples
analyzed under vacuum, and it can be used to monitor the beam current
when analyzing samples in air with an extracted beam.
C. Electronics
The experimental setup for the x-ray electronics during PIXE
analyse is shown in figure 1. The detector is an EG&G Ortec 7900
2
Si(Li), with 30 mm2 area, 8.0 pm Be window, and a FWHM resolution of
147 ev at 5.895 kev. The high voltage bias is supplied by an Ortec 459
power supply. An Ortec 972 spectroscopy amplifier and an Ortec 444
biased amplifier are used together for pulse-processing and dead-time
corrections. A Seiko EGG 7800 multi-channel analyzer with a Seiko 1820
ADC interface is used to collect the spectra. An Enertec 7143 linear
ratemeter is used to monitor the x-ray count rate. The charge induced
by the beam current is measured by a Brookhaven Instruments
Corporation 1000a current integrator, and stored in an Ortec 996
counter and timer.
In order to obtain a resolution of 147 ev on a real sample it is
necessary to keep the amplifier close to the detector (less than 3 m)
and to acquire the data with the vacuum pumps off. Mechanical
vibration from the pumps adds almost 15 ev to the resolution. (We are
working to better isolate the pumps from the target chamber.)
D. PIXAN reduction code
Since my experience with computers has been with DEC and Apple
computers, I have had to become familiar with SUN (UNIX) and IBM (DOS)
computers. PIXE spectra are analyzed on a SUN MS 3/260 workstation.
The computer program PIXAN is used to reduce an x-ray spectrum
to its elemental composition, and it does this in two parts. The first
part of the program calculates the areas of the characteristic peaks.
The background is subtracted and then the peaks are fitted to a
modified gaussian form. The area of the characteristic peaks are
directly proportional to the number of x-rays coming from the
characteristic elements. The second part determines the theoretical x-ray
yield given the composition of the sample and the energy of the
proton beam. It is then necessary to combine the results of the two
parts to get the elemental composition in parts per million (ppm). The
program is designed to be used for both thin and thick targets.
I have had to spend most of my time geting PIXAN to run
correctly. It is an excellent program, but it evolved over a long
period of time at the Australian Atomic Energy Commission. Thus it is
3
suited to the types of samples they analyze in Australia and the
experimental conditions in their laboratory. The results are
critically dependent on the x-ray detector parameters (crystal
diameter, sensitive depth, silicon dead-layer, and the gold electrode
layer), any external detector filters, the x-ray electronics, and even
the target composition (which determines the self-absorption/self-enhancement
effects). The most important step, and perhaps the most
difficult one, is a proper subtraction of the background continuum.
With PIXAN the background can be modelled either by a polynomial (up
to 5th order), or by an iterative method that removes the
characteristic peaks and progressively reduces the spectrum to the
background continuum. We have found that small changes in the
parameters used to model the background leads to large changes in the
final results. We have found that the iterative method works better
than the polynomial method for our samples, and have achieved results
on glass standards that are generally within 20% of the given values
for the elements Na to Pb (see section 4).
The exact experimental uncertainties are hard to determine. The
precision when measuring an element well above the limit of detection
and isolated from any interfering peaks is better than 5%. Elements
found near the limit of detection have greater uncertainties. Elements
with low energy x-rays (less than 2 kev) and high energy x-rays
(greater than 30 kev) have larger uncertainties since the detector
efficiency is quite low and poorly known in these regions. The case of
interfering peaks must be considered individually. For example, the
uncertainty in the measurement of sulfur (Ka = 2.307 kev) depends on
the amount of lead (Ma = 2.346 kev) in the sample. The overall
accuracy of a PIXE measurement depends on the uncertainties in the
following factors: the number of x-rays in a characteristic peak; the
number of incident protons; the detector efficiency; and the
absorption/enhancement corrections. In general, uncertainties of
around 10% - 20% can be expected with PIXE.
Most of the results to date have been determined without seeing
graphically the background or least-squares fit to the spectrum, a
most unfortunate circumstance. Thomas Calligaro has recently written a
program that displays the x-ray spectrum, the background, and the fit
4
of the data, an indispensible step in proper spectrum analysis. Good
spectrum analysis, even with the best computer programs, still
requires experience. One must know what to look for in the background
subtraction, the gaussian fit, the calculation of the sum and escape
peaks, the relative peak intensities, the unfolding of overlapping
peaks, and so forth. One must be careful and not simply accept the
results given by the computer program.
The data files included with PIXAN lacked some vital information
to make it work correctly for the samples we have at the Louvre, and
needed to be supplemented. First of all they did not include any M-line
x-ray data, which are necessary for quantitative results on the
elements Na through Cl (1-3 kev). We have therefore added M-line data
for Pb, Hg, Pt, and Au into the PIXAN data files. (The elements whose
M-line data is important for us to know immediately.) Secondly, the
data file of relative peak heights is appropriate only for 2.5 Mev
protons. The relative peak heights are important to know since PIXAN
uses them to untangle the overlap of peaks. Although the Ka/KB ratio
is independent of energy, the LalLi ratio, (where i is anyone of the
many other L-line x-rays), and the Ma/Mi ratios vary unsystematically
as a function of incident proton energy. Therefore it will be
necessary for us to modify the data tables for energies lower and
higher than 2.5 Mev in order to obtain the most accurate results. (We
will use the tabulated theoretical x-ray cross sections of D.D. Cohen
and M. Harrington, Atomic Data and Nuclear Data Tables 33, 1985, 255-
343.) Thirdly, L- and M-shell sum (pile-up) peaks are not included in
the peak search and are therefore not removed from the x-ray spectra.
The justification for not including the L- and M-shell sum peaks was
to make it easier for PIXAN to determine accurate amounts of Ti
(Ka=4.508 kev) and Ba (La=4.467 kev) when both are present in the
sample. However, L- and M-line pileup peaks are a serious problem when
a sample contains major or minor amounts of platinum, gold, mercury,
lead, tin, or barium.
III. RESULTS
We have acquired 52 PIXE spectra to date: 12 on glass standards,
36 on paint pigments, 3 on ceramic standards, and 10 on gold samples.
5
A. Glass
We have concentrated our efforts on four colored glass samples.
These samples have been well characterized, and they contain 27
elements between Na and Pb in quantities of 100 ppm to 35%. The
elements between Na and K (X-rays between 1 and 3 Kev) are difficult
to determine yet important in archaeometric studies of glass,
pigments, ceramics, and geological samples. In addition these glass
samples are ideal PIXE targets, being completely homogeneous, flat,
and small enough to fit into a vacuum chamber. We felt it was
necessary to get good results on these standards before we started
analyzing unknown targets.
The glass samples were prepared in 1964 by R. H. Brill and A. A.
Erickson of the Corning Glass Works in Corning New York. The four
samples were designed to duplicate the types of glass studied by
archaeologists and art historians. Two samples (known as Brill A and
Brill B) are soda-lime-silica glasses, which are similar to ancient
Egyptian, Mesopotamian, Ionan, Byzantine, and Islamic glasses. One
sample (Brill C) is a glass with high-lead and high-barium levels,
which is similar to glasses from Eastern Asia. The fourth sample
(Brill D) is a potash-lime-silica glass which is similar to certain
medieval glasses and some glasses of the 17th to 19th centuries. Minor
and trace elements were also introduced at levels that are comparable
to those actually found in ancient glasses. The method of fabrication
of these samples is given in R. H. Brill, A Chemical-Analytical Round-robin
on Four Synthetic Glasses, Proceedings of the IX International
Congress on Glass, Versailles 27 September, 1971.
The glass samples are several millimeters long and are embedded
in amber. They were analyzed at 1.0 and 2.5 Mev, with the intention of
obtaining the light elements (Na to Cal at 1.0 Mev, when there is no
detector filter, and the heavy elements (K to Pb) at 2.5 Mev, while
using a detector filter which allows the use of higher beam currents
and better (lower) sensitivity. The spectrum for Brill C at 2.5 Mev is
shown in figure 2 and the best results to date for the glass samples
are given in table 1. The element K was chosen to be an "internal
6
standard", so all the results are relative and normalized to the K
concentration. A comparison between the experimental resu
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