Paintings on copper

and other metal plates

PRODUCTION, DEGRADATION AND CONSERVATION ISSUES

La pintura sobre cobre

y otras planchas metálicas
PRODUCCIÓN, DEGRADACIÓN Y CONSERVACIÓN

Edited by
Laura Fuster López
Inmaculada Chuliá Blanco
M. Francisca Sarrió Martín
M. Luisa Vázquez de Ágredos Pascual
Leslie Carlyle
Jørgen Wadum
 Paintings on copper
and other metal plates
PRODUCTION, DEGRADATION AND CONSERVATION ISSUES

La pintura sobre cobre

y otras planchas metálicas
PRODUCCIÓN, DEGRADACIÓN Y CONSERVACIÓN

Edited by
Laura Fuster López
Inmaculada Chuliá Blanco
M. Francisca Sarrió Martín
M. Luisa Vázquez de Ágredos Pascual
Leslie Carlyle
Jørgen Wadum
Comité Científico y Editorial
Laura Fuster López
Departamento de Conservación y Restauración de Bienes Culturales, Universitat Politécnica de València (Valencia, Spain)
Inmaculada Chuliá Blanco
Subdirección del Institut Valencià de Conservació, Restauració e Investigació (IVC+R) de CulturArts Generalitat (Valencia, Spain)
M. Francisca Sarrió Martín
Subdirección del Institut Valencià de Conservació, Restauració e Investigació (IVC+R) de CulturArts Generalitat (Valencia, Spain)
M. Luisa Vázquez de Ágredos Pascual
Departamento de Historia del Arte, Universitat de València (Valencia, Spain)
Leslie Carlyle
Departamento de Conservação e Restauro and LAQV-REQUIMTE, Faculdade de Ciências e Tecnologia Universidade NOVA de
Lisboa (Campus da Caparica, Portugal)
Jørgen Wadum
Centre for Art Technological Studies and Conservation (CATS) (Copenhagen, Denmark)

Comité de redacción
Laura Fuster López
Elena Gandia Guijarro
M. Luisa Vázquez de Ágredos Pascual
Inmaculada Chuliá Blanco
M. Francisca Sarrió Martín
José Ignacio Catalán Martí

Portada
Laura Fuster López
Nico Broers

Imagen de portada
Cross section of a painting on copper from the collection of the Musée des Beaux-Arts de Liège (BAL).
(Foto: Nico Broers)

Diseño y maquetación
Antonio J. Ballester Sanz

Fotomecánica e impresión
LaimprentaCG

Edita
ComunicaCC

© de los textos, los autores Reservados todos los derechos. No se permite la reproducción total o parcial de esta obra, ni
© de las imágenes, sus autores su incorporación a un sistema informático, ni su transmisión en cualquier forma o por cual-
quier medio (electrónico, mecánico, fotocopia, grabación u otros) sin autorización previa y
ISBN: 978-84-16846-96-2 por escrito de los titulares del copyright. La infracción de dichos derechos puede constituir
Depósito Legal: V-191-2017 un delito contra la propiedad intelectual.
INDEX / ÍNDICE

Paintings on copper: An brief overview of their conception,

creation and conservation .............................................................................................................................. 17
Isabel HOROVITZ, The Painting Conservation Studio (London, UK)

The Spanish connection: The making and trade of Antwerp paintings

on copper in the 17th century .................................................................................................................... 27
Jørgen WADUM, Centre for Art Technologial Studies and Conservation CATS (Copenhagen, Denmark)

Reconstructing a painting on a copper support:

Hendrick van Balen’s ‘Adoration of the Shepherds’ from the Fitzwilliam Museum ......... 43
Alison STOCK, City & Guilds of London Art School (London, UK)

‘Silvered’ copper plates: A study of material, technique and function

of a rare metal support for paintings ........................................................................................................ 55
Anne SCHMID, Fondation Beyeler (Basel, Switzerland)

Preparation techniques and their impact on the conservation of copper paintings .......... 71
Nico BROERS, Ècole Saint Luc (Liège, Belgium)

Chemical, physical and mechanical decay processes in oil painted copper objects .......... 83
Lydia C. PAVLOPOLOU, Freelance Conservator, Bank of Greece external contractor (Athens, Greece)

A look into some factors influencing the film forming properties of oil paint films
in copper paintings and the effects of environment in their structural behaviour ............ 95
Laura FUSTER LÓPEZ, Universitat Politècnica de València (Valencia, Spain)
Marion F. MECKLENBURG, Smithsonian Institution (Washington D.C., USA)

A Saint Jerome after Palma il Giovane: artistic invention and the practice
of painting on copper in the age of printmaking ............................................................................... 103
Roxane SPERBER (Worcester Art Museum, USA), Anna Koopstra (National Gallery London, UK)

Creating An Enduring Image: An investigation into the materials and

techniques of the portrait of cardinal Antoine Perrenot de Granvelle
(1576, oil on copper) by Scipione Pulzone ........................................................................................... 111
Sally Higgs and Alexander J. NOELLE, Courtauld Institute of Art (London, United Kingdom)

5
La colección de pintura sobre cobre del Museo de Bellas Artes
de Santa Cruz de Tenerife .............................................................................................................................. 117
Antonio MARRERO ALBERTO, Freelance Conservator (Tenerife, Spain)
 
Recuperación de una valiosa colección de pintura flamenca realizada en cobre ................. 123
Rocío MAGDALENO GRANJA y Mª Auxiliadora GÓMEZ MORÓN, Instituto Andaluz
de Patrimonio Histórico (Sevilla, Spain)

Gerard ter Borch: copper versus canvas .................................................................................................. 131

Susanne STANGIER, Freelance Conservator (Guttecoven, The Netherlands)

Valoración científico-técnica de la pintura sobre cobre: casos de estudio .............................. 137

Inmaculada CHULIÁ BLANCO, Mª Francisca SARRIÓ MARTÍN y Livio FERRAZZA,
Subdirección de Conservación, Restauración e Investigación IVC+R de Culturarts-GVA (Valencia, Spain)
José Antonio MADRID GARCÍA, Universitat Politècnica de Valencia (Valencia, Spain)
Juan PÉREZ MIRALLES, Servicio de Conservación y Restauración de Bienes Culturales
de la Diputación de Castellón (Valencia, Spain)

Theoretical and practical considerations on the presence of lead soaps

in the degradation of an 18th century oil painting on a copper support ............................... 145
Filip Adrian PETCU, West University of Timişoara (Timişoara, Romania)

Análisis técnico-científico de una pintura sobre cobre del siglo XVIII.

Madonna con el Niño ........................................................................................................................................ 153
Guillermo MARTÍN QUESADA, Nuria GARCÍA-VALENZUELA PARERA
y Luis RODRÍGUEZ-SIMÓN, Universidad de Granada (Granada, Spain)

Proceso de restauración de dos pinturas sobre cobre del siglo XVIII procedentes
de los fondos pictóricos de la Diputación de Valencia .................................................................... 159
Cristina VÁZQUEZ ALBALADEJO, Adela MURGUI CERVERA y Aida RODA CIUDAD,
Diputación de Valencia (Valencia, Spain)

Conservation of a double-sided painting on copper plate in Lithuanian Art Museum .. 165

Ruta KASIULYTE, Lithuanian Art Museum Pranas Gudynas Restoration Centre (Vilnius, Lituania)

6
Investigations into paint delamination and consolidation of an oil painting
on copper ............................................................................................................................................................... 169
Maria Leonor OLIVEIRA, Leslie CARLYLE, Sara FRAGOSO and Isabel POMBO CARDOSO,
Universidade NOVA de Lisboa (Lisbon, Portugal)...............................................................................
João COROADO, Instituto Politécnico de Tomar, (Tomar, Portugal)
 
Reassessment of a consolidation treatment: Re-examination and conservation
of a persistent paint layer delamination on a 19th century tin-plated iron
support painting ................................................................................................................................................. 181
Christina KAPEUNDL, Anke SCHÄNING and Wolfgang BAATZ,
Institute of Conservation-Restoration, Academy of Fine Arts Vienna (Vienna, Austria)

Investigation and testing to develop an infill formula suitable for oil

paintings on copper .......................................................................................................................................... 187
Daniel VEGA, Isabel POMBO CARDOSO and Leslie CARLYLE,
Universidade Nova de Lisboa (Lisbon, Portugal)

Signposts from the collection of the Auschwitz-Birkenau State Museum ............................. 205
Gunn PÖLLNITZ and Manfred SCHREINER, Institute of Science and Technology in Art,
Academy of Fine Arts (Vienna, Austria)
 
Tracing back to antiquity: Materiality and meaning of ancient amulets
(metals and others) and sacred coloring materials in antiquity ................................................... 211
M. Luisa VÁZQUEZ DE ÁGREDOS PASCUAL and M. Julia MARTÍNEZ GARCÍA,
Universitat de València (Valencia, Spain)

7
 Desde la dirección del Departamento de Conservación y Restauración de la Universitat
Politècnica de Valencia, es motivo de doble satisfacción presentar esta publicación sobre el
simposio “La pintura sobre cobre (y otras planchas metálicas), producción, degradación y
conservación”, celebrado en la Universitat Politècnica de València el 27 y 28 de enero de 2017.
En primer lugar, por el hecho de haber trabajado conjuntamente en la organización del mismo
con dos instituciones con las que nos une un estrecho vínculo profesional e investigador como
es la Subdirección de Conservación, Restauración e Investigación de CulturArts (IVC+R) de
la Generalitat Valenciana y la Universitat de València (UV). En segundo lugar, y no necesaria-
mente en este orden, por la relevancia que sin duda este simposio va a tener para entender las
problemáticas relacionadas con este tipo de obras y hacer balance del estado de la cuestión a
nivel internacional.
Las instituciones que tenemos bajo nuestra responsabilidad la obligación de tutelar y for-
mar a los profesionales de la restauración, y de preservar y conservar el patrimonio cultural,
nos hemos unido en la organización de este evento que sin duda será un nuevo punto de
partida para establecer el estado de la cuestión en los tratamientos de láminas metálicas y su
interacción con otros materiales.
Una de las obligaciones de todos los que estamos involucrados en la conservación de obras
de arte es el intercambio de experiencias y el debate de criterios en torno a nuestras interven-
ciones, la reflexión sobre los dilemas éticos y los tratamientos que se aplican en problemáticas
similares en diferentes países. En este sentido, esta publicación recoge los trabajos e investiga-
ciones de profesionales de diferentes países, y constituye, por tanto, un compendio actualizado
de los tratamientos en el panorama internacional. Una gran parte de los estudios de pintura
sobre láminas metálicas centran el foco de atención en cuestiones de caracterización de mate-
riales y aspectos químicos, dejando en un segundo plano de interés los aspectos de interven-
ción práctica que tanto interesan al restaurador, así como otros aspectos relativos a su conser-
vación preventiva y manipulación. Estamos convencidos de que, en este sentido, las jornadas
serán especialmente fructíferas.
Asimismo, consideramos necesario agradecer a todos los que han querido compartir y ex-
poner sus trabajos y experiencias en estas conferencias, pues han hecho realidad esta iniciativa
y de ellos depende en definitiva el éxito de este simposio y de esta publicación.

Julia Osca Pons

Directora del Departamento de Conservación y Restauración de Bienes Culturales
Universitat Politécnica de València

9
 Esta publicación reúne la intensa labor desarrollada por los investigadores dedicados al
estudio de uno de los temas más desconocidos de las técnicas artísticas: la pintura sobre cobre
y otras planchas metálicas, así como su producción, degradación y conservación, y ello a pesar
de que su práctica estuvo muy extendida entre los artistas por la durabilidad de sus materiales.
La presente publicación es fruto del marco de colaboración establecido entre la Universi-
tat Politècnica de València, la Universitat de València y la Generalitat Valenciana a través del
Institut Valencià de Conservació i Restauració. En este sentido, queremos agradecer a las dos
universidades el haber contado con nuestro centro para el desarrollo de esta actividad, que
potencia aún más nuestra vertiente investigadora.
La oportunidad brindada al Institut Valencià de Conservació i Restauració de participar en
la organización del simposio internacional, ‘La pintura sobre cobre (y otras planchas metálicas).
Producción, degradación y conservación”, ha sido uno de los muchos proyectos de investigación
y formación a los que hemos dedicado un especial esfuerzo y atención, ya que en él van a par-
ticipar conservadores, restauradores, científicos, historiadores del arte y perfiles profesionales
afines de todo el mundo, dedicados a este singular tipo de patrimonio.
Estos encuentros internacionales permiten establecer vínculos de conexión e intercambio
de conocimientos entre profesionales dedicados a la conservación, estudio y preservación del
patrimonio artístico de otras partes del mundo, pero siempre buscando un fin común: la
salvaguarda del Patrimonio artístico. Y es precisamente ese espíritu el que queda recogido en
esta publicación para su conocimiento y difusión. En este sentido, nos gustaría dar un recon-
ocimiento especial a Isabel Horowitz, Jørgen Wadum, Nico Broers, Lydia Pavlopoulou, Leslie
Carlyle, Alison Stock, Anne Schmidt y Lucía Martínez, por su contribución a este encuentro
con sus interesantes aportaciones.
El enfoque multidisciplinar y metódico de la conservación de estas obras permitirá un
conocimiento más profundo de su degradación, de su alteración y de los mecanismos de
deterioro, que han sido poco estudiados en el pasado, y que, con estas jornadas y publicación,
queremos subsanar esa carencia bibliográfica y documental con la que muchas veces nos
encontramos a la hora de afrontar una intervención en una obra de estas características.
Gracias a este encuentro podremos acercarnos mejor a los aspectos histórico-artísticos de la
producción pictórica sobre plancha metálica; a la caracterización de los materiales presentes en
la pintura sobre cobre u otro tipo de metal; a la interacción entre películas pictóricas de origen
natural o sintético y el sustrato metálico; así como a los tratamientos de conservación de obras
pictóricas realizadas sobre este tipo de soporte.
Desde el Institut Valencià de Conservació i Restauració de la Generalitat Valenciana
deseamos que esta publicación sea de gran ayuda y utilidad para todos aquellos profesionales
del campo de la restauración que se dedican al estudio e investigación de las obras de arte
pintadas sobre cobre u otro soporte metálico.

Gemma María Contreras Zamorano

Subdirectora del Institut Valencià de Conservació i Restauració
IVC. Generalitat Valenciana

11
La colaboración entre disciplinas e instituciones como herramienta esencial para la Historia
del Arte y la conservación preventiva

En los días 27 y 28 de enero del 2017 tendrá lugar el Symposium Painting on Copper cele-
brado en Valencia como fruto de una estrecha colaboración entre la Universitat Politécnica de
Valencia, la Generalitat Valenciana a través de la Subdirección de Conservación, Restauración
e Investigación (IVC+R) y la Universitat de València, a través de la Facultat de Geografia i
Història y, en concreto, con la colaboración de su Laboratorio en Historia del Arte para el
Análisis y Diagnóstico de Obras de Arte.
La triangulación de estas tres entidades valencianas se desvela como una acción no solo
necesaria, sino fundamental e imprescindible para la buena ejecución de proyectos sólidos y de
calidad en los tres ejes fundamentales vinculados a la conservación, el estudio y la restauración
de las obras de arte, como lo son la docencia, la investigación y la difusión de los resultados. A
ello se une la praxis directa sobre la obra de arte en sí, cuyo planteamiento desde la conserva-
ción preventiva, el análisis histórico y científico o la restauración requiere, y hoy más que
nunca, de una visión conjunta y multidisciplinar que permita la realización de trabajos trans-
versales que contribuyan al avance del conocimiento. Por ello, este primer convenio firmado
por las tres entidades supone un significativo hito en la historia de la colaboración universita-
ria y la administración pública valenciana
El Symposium Paintings on Copper pretende acercar y reunir a los principales especialistas
en el estudio y análisis de la pintura en soporte de cobre y otras planchas metálicas, y servir de
encuentro entre conservadores-restauradores, científicos de la conservación e historiadores del
arte con el objetivo de poner en común las principales novedades y los estudios realizados
desde la óptica de cada una de las disciplinas bajo perspectivas de perfil interdisciplinar. Hoy
más que nunca es necesario hacer hincapié en la necesidad de estos trabajos en conjunto, pues
son los que permiten una correcta actuación sobre los bienes culturales. Para lograr esa meta
anhelada se erige como imprescindible el desarrollo de una labor de investigación científica y
documental que permita documentar la obra y los procesos acometidos, conocer la naturaleza
física de las obras de arte y las fuentes históricas que la documentan, así como su correcto
análisis histórico-artístico vinculado a su vida cultural. Sólo este conocimiento riguroso y ex-
haustivo, que va más allá de la recopilación y cobra una singularidad heurística, es la que
sentará las bases del respeto a los valores añadidos que toda obra presenta, el Alterweist, o valor
de los antiguo que permite comprender cualquier bien artístico como el resultado de un sedi-
mento físico acumulativo de la actividad humana, pues encierra en sí valores culturales, mate-
riales y técnicos.
El trabajo del historiador del arte junto a los profesionales de la restauración y la ciencia de
la conservación no puede sino contribuir a enriquecer el estudio y la investigación, objetivos
que por sí mismos, de manera aislada son significativos, pero que deben trascender el mundo

13
de la academia y aproximarse a la sociedad: enseñar, divulgar, defender y conservar el patrimo-
nio artístico, en definitiva, todo lo que tiene que ver con el moderno concepto de “Patrimonio
Cultural” -del que el artístico constituye una porción substancial, debe favorecer la creación de
puentes conjuntos en la construcción de equipos en los que el historiador del arte ha de estar
presente en todas las tareas relacionadas con la custodia o tutela del Patrimonio, desde su co-
nocimiento hasta su gestión, pasando por su conservación, siquiera sea porque las decisiones
acerca del patrimonio artístico en cualquiera de esos niveles han de estar basadas en la com-
prensión histórica de las obras de arte.
Por ello, la importancia de la Historia del Arte se incardina profundamente dentro de lo
que Lafuente Ferrari definió como las Humanidades visuales, en el sentido que la historia del
arte supone para el hombre del siglo XX algo así como las humanidades del presente, unas
humanidades visuales que han venido a desplazar, en cierto modo–con lo que ello supone de
importantes consecuencias, para bien y para mal–, a las humanidades clásicas: a las letras pro-
piamente dichas han sucedido las imágenes. Ello otorga singular entidad a la orientación del
trabajo del historiador del arte, así como a las cuestiones generales de fundamentación de una
disciplina que ha alcanzado parte tan capital en la formación cultural del hombre de hoy.
Como ha postulado Jacques Derrida las Humanidades por venir atravesarán las fronteras entre
las disciplinas sin que eso signifique disolver la especificidad de cada disciplina dentro de lo
que se denomina a menudo de modo confuso la interdisciplinariedad; pues lo realmente ne-
cesario es la creación de redes, la investigación colaborativa y el establecimiento de objetivos
comunes en un proceso dialógico constante.
Este primer paso fundamental, con la firma del convenio que da lugar a este Symposium,
inicia un camino que, aunque transitado, a menudo se ha perdido en sendas desdibujadas o
laberínticas. Esperamos que, ahora sea el inicio de otra manera de construir nuevas sendas,
basadas en el respeto, la colaboración y la construcción de un futuro común en el que el obje-
tivo sea la correcta salvaguarda de algo tan nuestro como lo es el arte y los testimonios que la
creatividad de hombres y mujeres de nuestro ayer nos ha preservado, y los que hoy siguen
construyendo y creando los artistas contemporáneos como parte fundamental en la compren-
sión cultural de lo que somos.

Ester Alba Pagán

Degana de la Facultat de Geografia i Història
Unversitat de València

14
 This publication accompanying the international symposium, “Paintings on copper and
other metal plates. Production, degradation and conservation issues”, organized jointly by the
Universitat Politècnica de Valencia (UPV), the Universitat de València (UV), and the Subdi-
rección General del Institut Valencià de Conservació, Restauració e Investigació IVC + R de
CulturArts Generalitat, will be covering a wide range of issues relating to the making and
preservation of paintings on metal.
Paintings on copper and other metal plates have long been valued as refined and elegant
works of art. The practice of painting on copper seems to have appeared in Florence in the
third quarter of the sixteenth century and was taken up as a specialty by the circle of Paul Bril
in Rome in the 1590s. From there the practice spread, in particular to Prague, Antwerp and
Utrecht, but its popularity waned after 1650.
Other metal supports would, in the second half of the 17th century, continue to be em-
ployed for large church decorations, such as the lead-tin alloy used for the impressive almost
7 x 4 m altar in St. Stephan’s cathedral in Vienna which is composed of 36 sheets soldered
together. Equally, tinned-iron plates were used by artists late in the 18th century in Austria,
and we still find copper and other metal plates in occasional use for painting supports well
into the 19th century.
We may be able to divide paintings on copper and other metal supports into two distinct
groups: one motivated by practical concerns, the other by aesthetic goals. Copper or other
metals, relatively light-weight and easily transported, were ideal for images such as portraits
and religious scenes that needed to travel, (and we see evidence of this travel, particularly from
Antwerp, to Spain and from there to the Americas). The second group consists of works by
artists of the highest caliber, for whom the choice of copper clearly had artistic meaning.
As a durable, compact support, copper was ideal for mass-produced paintings intended for
export; usually the work of minor or anonymous artists, and often reproducing famous com-
positions. Despite the availability all over Europe and the New World from early in the 16th
century of prints made from copper engravings, paintings directly on copper and other metals
documented colour and handling beyond what prints could convey.
Both small and large copper plates, as well as composite metal supports, each convey new
and challenging preservation issues based on their materials and techniques and/or the envi-
ronment in which they have been kept.
It is our ambition that this publication will provide an enduring record -although possibly
not as durable as the metal sheets themselves-, of the timely and rich discussions between the
conservator-restorers, conservation scientists, art historians and other professionals who were
assembled together during this symposium in Valencia.

15
 Esta publicación es el resultado del simposio internacional ”Pinturas sobre cobre y otras planchas
metálicas. Producción, degradación y conservación”, organizado conjuntamente por la Universitat
Politècnica de Valencia (UPV), la Universitat de València (UV) y la Subdirección General del
Institut Valencià de Conservació, Restauració e Investigació IVC + R de CulturArts Generalitat, y
en ella se aborda una amplia gama de temas relacionados con la fabricación y conservación de obras
pictóricas sobre plancha metálica.
Las pinturas sobre cobre y sobre otras planchas metálicas fueron concebidas como obras de arte
refinadas y elegantes. La práctica de la pintura sobre cobre parece surgir en Florencia en el tercer
cuarto del siglo XVI llegando a ser una especialidad en el círculo de Paul Bril en la Roma de 1590.
Desde allí la práctica se extendió en particular a Praga, Amberes y Utrecht, aunque su popularidad
disminuiría a partir de 1650.
En la segunda mitad del siglo XVII se seguirían empleando otros soportes metálicos para deco-
raciones de grandes iglesias, como la aleación de plomo-estaño utilizada en el impresionante altar
de casi 7x4 m de la catedral de San Esteban de Viena, compuesta por treinta y seis planchas soldadas
entre sí. Del mismo modo, algunos artistas utilizaron planchas de hierro estañado a finales del
siglo XVIII en Austria, e incluso encontramos cobre y otras planchas metálicas de uso ocasional como
soporte pictórico hasta bien entrado el siglo XIX.
Podemos dividir la pintura sobre cobre y otros soportes metálicos en dos grupos diferenciados:
uno motivado por preocupaciones de índole práctico, y un segundo grupo motivado por aspectos de
carácter estético. El cobre u otros metales, relativamente ligeros y fácilmente transportables, result-
aban ideales para retratos y escenas religiosas que necesitaban viajar (viajes bien conocidos, especial-
mente de Amberes a España y de allí a las Américas). El segundo grupo consiste en obras de artistas
del más alto nivel, para quienes la elección del cobre tenía claramente un significado artístico.
Como soporte duradero y compacto, el cobre era ideal para pinturas producidas en serie destina-
das a la exportación; se trataba generalmente del trabajo de artistas menores o anónimos, que a
menudo reproducían composiciones conocidas. A pesar de la disponibilidad de grabados realizados
a partir de planchas de cobre en Europa y el Nuevo Mundo desde principios del siglo XVI, la pin-
tura realizada directamente sobre cobre y otras planchas metálicas dan buena cuenta del uso del
color y de las habilidades técnicas mucho más allá de lo que los grabados podían transmitir.
Tanto las planchas de cobre pequeñas como las grandes, así como los soportes metálicos, repre-
sentan nuevos desafíos y problemas de conservación debido a los materiales y técnicas empleados es
su producción y/o al entorno en el que se han preservado.
Esperamos que esta publicación se convierta en un documento duradero -aunque posiblemente
no tan duradero como las propias planchas de metal-, de las oportunas y ricas discusiones entre
conservadores-restauradores, científicos de la conservación, historiadores del arte y otros profesion-
ales que se han dado cita en este simposio en Valencia.

Valencia (España) 17 Enero 2017 - Valencia (Spain) 17 January 2017

Jørgen Wadum
Leslie Carlyle
Laura Fuster López
M. Luisa Vázquez de Ágredos Pascual
M. Francisca Sarrió Martín
Inmaculada Chuliá Blanco

16
 Investigation and Testing to Develop an Infill
Formula Suitable for Oil Paintings on Copper

Daniel VEGA
Departamento de Conservação e Restauro
Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Monte da Caparica, Portugal
Isabel POMBO CARDOSO
Departamento de Conservação e Restauro & Requimte-CQFB
Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Monte da Caparica, Portugal
Leslie CARLYLE
Departamento de Conservação e Restauro & Requinte-CQFB
Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Monte da Caparica, Portugal

Abstract Introductio

This paper focuses on finding an inert formulation
for pigmented wax-resin infills to be used for oil paint-
ings on copper. Two pigmented wax-resin formulations
currently in use are characterised: one supplied by one of
the authors (C-PWR) and the other, a commercial prod-
uct, Gamblin Pigmented Wax-Resin sticks (G-PWR).
While both have excellent properties, they contain natu-
ral beeswax which has been reported to result in corro-
sion where in contact with copper. Acid number mea-
surements confirm that both are acidic. Although ageing
tests are still needed, the characterization and properties
of two new formulations, both based on Techniwax
9426 microcrystalline wax with either Regalrez 1094 or
1126, are promising. Both new wax-resin mixtures, with
an acid number of 0, are likely to be inert in relation to
the copper and are anticipated to be chemically stable
due to their composition.
Keywords: oil painting on copper, infills, wax-resin, mi-
crocrystalline wax, synthetic resins, beeswax
It has been reported that paint losses on oil paint-
ings on copper result from a chemical reaction be-
tween the copper support and the oil paint composite
which includes both ground and paint layers (Horo-
vitz 1986, 1996, 1999; Pavlopoulou 2004; Pavlopou-
lou & Watkinson 2006). This was reinforced by ob-
servation of over 80 oil paintings on copper where
losses tended to be complete, leaving the metal un-
derneath exposed (Vega 2016) (Fig. 1a&b). While
the primary reason for re-integrating paint losses by
infilling and inpainting is to restore unity to the im-
age, there is also an argument for this step, as a means
to reduce or halt further corrosion of the exposed
metal (Phipps & Rice 1979; Zakipour et al. 1995;
Grzywacz 2006).
A review of publications on infill materials in use
or under consideration (see below) led to the conclu-
sion that pigmented wax-resin could offer significant
advantages over previous options. However, formula-

139
 DANIEL VEGA – ISABEL POMBO CARDOSO – LESLIE CARLYLE
tions in use for oil paintings on other supports nor-
mally contain beeswax, which has been shown to cor-
rode copper (see below). Therefore, one of the aims of
the Masters thesis work described here, which was car-
ried out by Daniel Vega at the Universidade Nova de
Lisboa, was to develop a non-acidic pigmented
wax-resin mixture (Vega 2016).
Properties of an ideal infill material
In her PhD thesis on infill materials for the conser-
vation of paintings (2006), Laura Fuster López identi-
fied the ideal properties of a successful infill (76-77):
– compatible with the original materials (chemi-
cally, physically and mechanically);
– capable of receiving an impression of texture (if
necessary);
– stable to relative humidity and temperature
fluctuations;
– removable mechanically (or at least removability
is restricted to mild aliphatic solvents); and
– long term physical and chemical stability.
In addition, infills for oil paintings on copper should
also be capable of being applied in very thin layers to
match the thickness of the paint composite (thin paint/
ground layers are reported by Horovitz 1999; Rizzo
2008; Broers 2002 and Vega 2015 see fig.1 a&b). As
will be seen, a non-acidic pigmented wax-resin would
fullfill these ideal properties.
Table 1.
Published treatments of losses for oil paintings on copper
Authors Isolation Layer
Leegenhoek, 1986 Varnish
Garrel, 1992
Scott-Moncrief, 1993
Berger, 1995 Microcrystalline wax + UVS
Retouch varnish
Maule, 2002 B-72:B-48 + acetone
Broers, 2002 B-72 + xylene + BTA
n.aq = non aqueous; aq = aqueous. See Appendix 1 for the identity of materials where known
140
Overview of previous infill materials
The literature falls into two categories: those cover-
ing treatments (Table 1); and empirical trials with dif-
ferent infill materials (Table 2).
Table 1 demonstrates that most of the infills used
were aqueous based. To act as a water barrier prior to
the application of the infill, isolating layers were used in
four of the six treatments. Tables 1 & 2 indicate that the
acrylic co-polymer Paraloid B-72 was used most fre-
quently for this. In empirical trials, (Table 2) Horovitz
looked at three non-aqueous options, however she re-
ported problems with adhesion and handling during
application. Table 2 shows that some non-conservation
products were reported to perform well but the lack of
information on their ingredients and the impossibility
of assuring that the same formulations will be used by
the manufacture beyond the product tested at the time
of publication, means that these commercial materials
cannot be relied on, either in terms of their longevity, or
in terms of repeatability.
The Corrosive Action of Beeswax on Copper
Two authors, Leegenhoek 1986, and Garrel 1992,
refer to beeswax as an infill ingredient (Table 1). How-
ever, Horovitz (1996) reported that in her trials beeswax
promoted corrosion on copper. Beeswax’s corrosive ac-
tion on copper and copper alloys is reported elsewhere
in the conservation literature (Webb 2000; Scott 2002).
Infill Type
Infill Materials
n. aq aq
Hide glue + CaCo3 X
Beeswax + CaCo3
X
Beeswax X
Fine Surface Polyfilla X
Mowilith 20 + solvents + pigments X
Gelatine putty X
Lascaux Hydro-Grund 750 + pigments X
 INVESTIGATION AND TESTING TO DEVELOP AN INFILL FORMULA SUITABLE FOR OIL PAINTINGS ON COPPER

Table 2.
Summary of empirical trials by Horovitz, Broers and Rizzo

Authors Isolation Infill Materials Infill Type Author’s Observations

Layer n.aq. aq.
Horovitz, B-72 B-72 + chalk X Unsatisfactory to apply, and may be disrupted
1996 by B72 isolating layer
Plextol B500 + chalk X Adhesion is difficult
Beva 371 + chalk X Spontaneously peeled off upon drying
Fine Surface Polyfilla X Useful where coarse texture is required
Rowney Acrylic X Suitable for shallow losses but rubbery and
difficult to carve
Liquitex Acrylic X Very spreadable, suitable for large flat areas of
Gesso shallow loss
Broers, B-72 + BTA Lascaux X Easy to apply and carve
2002 Hydro-Grund 750
Rizzo, B-72 Modostuc X Good performance
2008 Gel Relief X Easy to apply; suitable when textured surfaces
(Lefranc & Bour- are required.
geois ) Become transparent after drying
Tempera paint X Fills up the loss with several applications
n.aq: nonaqueous; aq.: aqueous. See Appendix 1 for the identity materials where known

Scott (2002) explains that carboxylic groups from the
fatty acids present in beeswax interact with metal ions
from the copper resulting in the formation of copper
soaps (metal carboxylates). These organometallic com-
pounds are reported to be chemically unstable, to attack
metallic copper, and to promote further corrosion (Pat-
erakis 1996, 2003; Scott 2002). Since four of the five
fatty acids in beeswax, palmitic, linoleic, stearic, and
oleic, are the same as the major fatty acids in drying oils
(van den Berg 2002), it follows that beeswax would
have a similar effect on copper as drying oil. Drying oil
is reported to form a green corrosion layer at the inter-
face between the oil layers and the copper (Pavlopoulou
& Watkinson 2006; Oliveira 2015).
Pigmented wax-resin infills
Mixtures of wax and resin (natural or synthetic) in
different proportions with the addition of pigments and
fillers have resulted in infill materials that are highly ver-
satile. Pigmented wax-resins (PWRs) were traditionally
produced by conservators themselves. In recent years,
pigmented and unpigmented wax-resin sticks have been
manufactured for conservation use by Robert Gamblin
(gamblincolors.com/conservation-colors). Gamblin’s
formulation, which will be described below, is based on
research by Christine McIntyre for her Master’s thesis at
Buffalo State College (McIntyre, 2011).
For infills on copper, PWR has several advantages: it
is non-aqueous and is likely to remain relatively imper-
meable to moisture. PWR can be easily introduced in
the form of a fluid or a paste. It is capable of forming a
very thin layer that does not shrink or crack (in the con-
text of the inflexible copper support, mechanical crack-
ing is not anticipated). For texturing, the fill can be
shaped while warm, carved when cold, or the surface
can be modified using a solvent with a low aromatic
content (e.g. white spirit). It is easily removed mechan-
ically or by using a solvent. Empirical trials indicate
very effective adhesion to the copper metal.
However, because the current formulations for
wax-resin infills commonly contain beeswax, they have
not been considered appropriate for paintings on cop-
per. Furthermore, blooming, the development of a thin
whitish crystalline layer, has been reported on the sur-
face of some of these PWRs. Bloom is associated with

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 DANIEL VEGA – ISABEL POMBO CARDOSO – LESLIE CARLYLE
beeswax, and has been reported on encaustic paintings,
sculptures, and wax seals (Harley 1993, Novotna &
Dernovskova 2002, Bartl et al. 2015). Several studies
have been carried out to establish the mechanism of
blooming (Bartl et al. 2012, 2013, 2015). The most re-
cent indicate that blooming is related to the migration
and recrystallization of alkenes naturally occurring in
beeswax (Bartl et al. 2015)1 Studies on whether bloom
will migrate through layers of pigmented resin used in
inpainting on top of pigmented wax-resin fills has have
not been found.
Because of the significant advantages presented by
PWR infills, it was decided to explore the possibility of
finding a formulation which would eliminate the need
for beeswax. To act as references for the characteristics
sought in the new formula, two successful wax-resin
formulations were chosen: a formula used by Carlyle in
the early 1980s (C-PWR) and Gamblin’s Pigmented
Wax-Resin sticks (G-PWR). Both reference formula-
tions contain beeswax.
Wax-resin infill formulations
Various authors (Murta 2007; Kemp 2009; Fuster
López 2012) report that throughout the 20th century,
formulations based on mixtures of natural waxes and
resins with pigments and fillers have been used exten-
sively as an infill material for easel paintings and for
other cultural objects. Fuster López notes the substi-
tution of natural resin with a synthetic which oc-
curred most likely after the 1950s, when cyclohexa-
none resin (originally Ketone Resin N, later Laropal
K 80) was introduced (Fuster López 2012). PWR in-
fills using beeswax with Ketone Resin N were in use at
the Canadian Conservation Institute in the early
1980s2 and a PWR formulation using beeswax, a mi-
crocrystalline wax, ‘Be SquareTM 195’ and Larapol K
80 was used at Buffalo State College (McIntyre 2011).
For her master thesis, McIntyre explored new PWR
formulations aiming to find a substitute for Laropal K
80 after its manufacture by Badische Anilin- und So-
da-Fabrik AG (BASF) was discontinued in 2008
(McIntyre 2011). As noted above, her research was
later used by Robert Gamblin in trials which resulted
in his PWR sticks.
The PWR samples from Carlyle (C-PWR) consist of
four parts beeswax to one part Ketone Resin N. Dry
pigment and chalk (calcium carbonate) were added to
142
the melt until the right consistency was achieved (the
consistency is very similar to G-PWR below). Carlyle
provided three PWRs which had been prepared in the
early 1980s: a titanium white, a burnt umber and an
unpigmented sample.
Gamblin’s Pigmented Wax Resin Sticks (G-PWR)
were purchased in 2009 and 2015. They consist of 3
parts beeswax, one part Be SquareTM 195 and one part
Laropal A 81 (a urea aldehyde resin). Dry pigment is
added in a proportion of one part pigment to one part
WR by weight.3 For the present study, sticks labelled
Titanium white, Burnt Umber and Neutral Base (an
unpigmented stick) were chosen for direct comparison
with the C-PWR samples.
The individual ingredients
Waxes
Beeswax shows differences in composition depend-
ing on the species and their food supply (Tulloch 1980,
Aichholz & Lorbeer 1999, 2000a). Tullock reported
that beeswax generally consists of: 14 per cent hydrocar-
bons (alkanes and alkenes), 35 per cent monoesters, 14
per cent Diesters, 3.3 per cent Triesters, 3.6 per cent
Hydroxy monoesters, 7.7 per cent Hydroxy polyesters,
12 per cent free fatty acids, 0.8 per cent acid monoesters
and 8.6 per cent of unidentified compounds (Tulloch
1980). These concentrations vary slightly depending
upon the analytical procedures applied (Tulloch 1980;
Aichholz & Lorbeer 1999, 2000a&b; Jiménez et al.
2004). Mills & White report a melting point for bees-
wax of 63-64ºC and softening point of 49 - 53.3 ºC
(Mills & White 1999). Tulloch (1980) reports an acid
value of between 16 and 24, however much higher acid
values have been reported, from 16 to 125 (Warth
1956). Beeswax can be purchased either refined or un-
refined. Acid treatments used during refining are re-
ported to have little effect on the original acid value
(Warth 1956).
Of the synthetic waxes which have been used in
some PWR formulations along with beeswax, and are
candidates to replace beeswax in the new PWR formu-
lation, there are two groups: macro-crystalline (e.g. par-
affin) and microcrystalline waxes (ManSoori et al.
2003). The paraffins tend to be brittle and are therefore
not suitable (Crowley & Laefer 2008, Laefer et al.
2015); leaving the microcrystalline waxes. Pillon re-
ports on their composition: 30-60 carbon atoms and an
 INVESTIGATION AND TESTING TO DEVELOP AN INFILL FORMULA SUITABLE FOR OIL PAINTINGS ON COPPER
average molecular weight of 500-800 g/mol, with 0-15
wt per cent of n-paraffins; 15-30 wt per cent of iso-par-
affins (branched); and 65-75 wt per cent of naphthenes.
The melting point of microcrystalline waxes range from
60 to 90ºC (Pillon 2008).
Resins
Resins usually have a medium molecular weight,
an amorphous and often complex structure; and like
waxes, they do not exhibit a precise melting point
(Mildenberg et al. 1997). Synthetic resins cover a wide
range of materials obtained by the polymerization of
hydrocarbons. René de la Rie, has extensively studied
synthetic resins suitable for conservation use primarily
in relation to painting varnishes (de la Rie & Mc-
Glinchey 1990, de la Rie et al. 2002, Maines & de la
Rie 2005).
As noted above, one of the first synthetic resins to
replace dammar resin in PWRs was cyclohexanone, but
it is no longer made. For this work, along with the Lara-
pol A 81 used in McIntyre’s formula, three other syn-
thetic resins were tested for the new wax-resin formula-
tion: Laropal A 110, and Regalrez 1094 and 1126 (these
resins, introduced by de la Rie were chosen based on
stability testing as well as their easy availability). Laropal
A, developed by BASF, is obtained by the condensation
reaction between urea and aliphatic aldehydes (Von der
Goltz et al. 2012). Information combined from de la
Rie et al. 2002, Maines & de la Rie 2005, and online
BASF Safety Data sheets January 2016, provide the fol-
lowing: the molecular weight (MW) of Laropal A 81
ranges from 3640 to 4300; the glass transition tempera-
ture (Tg) is 57ºC; and the melting range (m.r.) is be-
tween 80-95 ºC. Laropal A 101 has a much lower MW:
2979, and a higher Tg: 73 ºC. The melting range is also
higher: between 95-110 ºC.
Regalrez, developed by Hercules Inc. (and currently
produced by Eastman Chemical Co), is a low molecular
weight resin resulting from the polymerization of hy-
drogenated styrene monomers. The chief difference be-
tween Regalrez 1094 and Regalrez 1126 is their molec-
ular weight. This modifies their properties: Regalrez
1094 has an average MW of 900 g/mol, a Tg of 41 ºC
and melting point of 95 ºC; whereas Regalrez 1126 has
an average MW of 1250 g/mol, a Tg of 67 ºC and a
melting point of 124 ºC. Regalrez 1094 has a lower vis-
cosity than Regalrez 1126 (de la Rie & McGlinchey
1990; Regalrez® 1094 & 1126 datasheets).
Experimental: a comparison with reference PWRS
and the new formulations
Both PWR reference samples demonstrated excel-
lent performance with very similar working properties
in terms of application and adhesion to copper sub-
strates, therefore the aim was to match their key proper-
ties in the new formulation.
Unpigmented samples were studied first, so that re-
sults would not be masked by the presence of pigments
or filler. The same tests were then used to study the pig-
mented versions, and all tests were then applied to the
new formulations for comparison. Physical/chemical
investigations included: chemical characterization by
Micro Fourier Transform Infrared Spectroscopy
(μ-FTIR) and FTIR- Attenuated Total Reflectance
(FTIR-ATR), melting range, glass transition tempera-
ture (Tg), and acid number. Other important parame-
ters for determining the suitability of the infills were:
workability, removability, and hardness.
Chemical characterization
μ-FTIR and FTIR-ATR analysis were carried out on
the PWR reference samples, the new pure materials,
and new formulations, to establish their composition
and evaluate their durability based on the compounds
present. Spectra acquisition for both methods are de-
scribed in Appendix 2, for the spectra see Figs 3.1, 3.2,
3.3 in Appendix 3.
Melting range and Tg
A Reichert Thermovar melting point microscope
(Appendix 4) was used to determine the melting range
of the materials. These measurements establish the tem-
perature at which the PWR is workable. Softening
point cannot be close to room temperature, since that
would incur the risk of future deformation/distortion in
ambient conditions, and the melting point cannot be
too high since the PWR must be safely applied without
the potential to cause heat damage to the paint. The use
of this instrument involved observation during con-
trolled heating: the temperature was registered when
the material flows for the first time (softening point)
until the moment it becomes completely liquid (melt-
ing point).
Similarly, the glass transition temperature (Tg) is
important: a Tg close to room temperature indicates a
143
 DANIEL VEGA – ISABEL POMBO CARDOSO – LESLIE CARLYLE
material which is soft and flexible but susceptible to dirt
absorption, while a high Tg is associated with brittle
materials (Horie, 2010). Tg and melting range can be
established using ASTM 4419 with Differential Scan-
ning Calorimetry (DSC). DSC also provides data relat-
ed to the degradation temperature of the PWRs. At the
time of writing results were not yet available but DSC
measurements are being planned for the near future.
Acid number
ASTM D1386 describes the procedure for deter-
mining the acid number of waxes and was used for test-
ing the PWR reference samples and wax-resins being
considered for the new PWR formulation. The acid
number is determined by the number of milligrams of
potassium hydroxide (KOH) necessary to neutralize
one gram of sample dissolved in solvent. In the study
being reported here, this correlates to the presence of
carboxylic groups derived from fatty acids in beeswax.
Details of the procedure from ATSM D1386 are repro-
duced in Appendix 5.
Workability
Two fragments from old oil paintings on copper
thought to date from the 18th century4 were used for
testing the workability of the PWRs. Some of the paint
composite losses on the fragments were isolated first us-
ing Paraloid B-72 diluted in toluene (15 per cent w/v).
PWRs were heated and applied to losses with and with-
out the isolation layer using a ‘wax carving pencil’ (Ap-
pendix 4.).
Removability
Mechanical removal of the different PWR infills was
tested using a wooden stick. Two mild aliphatic solvents
(Shellsol D and white spirit) were also tested for remov-
al using solvent.
Hardness
The hardness of the PWR is an important parameter
for judging its suitability. Extremely hard substances
would not be appropriate for filling losses surrounded
by oil paint composites with significantly different
physical properties. The ASTM International standard
for measuring the hardness of waxes is D1321 which
requires a penetrometer. Unfortunately, it was not pos-
144
sible to gain access to this instrument in Portugal.
Therefore, empirical testing using a needle to penetrate
the surfaces of the PWRs was used. Hardness testing
was carried out by one individual to achieve a level of
uniformity in the results.
The selection of waxes, resins and pigments for
the new formulation
Five microcrystalline waxes were chosen based on
their melting ranges which were similar to the ingredi-
ents in the PWR reference samples. The British compa-
ny Kerax (kerax.co.uk), kindly provided samples for this
study with the melting ranges required (Table 3).
McIntyre found Laropal A 81 to be the best option
for replacing Ketone Resin N in the PWR formula she
was using, as it provided effective adhesive qualities and
flexibility (McIntyre 2011). For this research Laropal A
101 was also investigated to explore the effect of chang-
ing MW and melting range.
McIntyre had eliminated Regalrez 1094 because she
found that it made a slightly brittle WR which did not
mix well with pigments. In the present study Regalrez
1094 was included because different microcrystalline
waxes were being tested which could improve its perfor-
mance. Because Regalrez 1094 is reported to exhibit
long-term stability (de la Rie & McGlinchey 1990,
Smith & Johnson 2008) and is currently widely avail-
able, a re-evaluation was felt to be important. Regalrez
1126 was included to establish whether it would pro-
vide any advantages over Regalrez 1094 (Table 4).
The ratio of wax to resin and the procedure for combining
materials
McIntyre’s successful formula, adopted by Gamblin,
called for four parts wax to one part resin by weight.
Therefore, initial trials for the new formulation were
based on this ratio (which turned out to give good con-
sistency with the new formulations). Guidelines from
McIntyre’s thesis for producing the mixtures were fol-
lowed (McIntyre 2011) with further advice provided by
Robert Gamblin (via email correspondence).
Materials were weighed on a digital precision bal-
ance (Appendix 4). The wax was melted using a
bain-marie, and the resin, which had been reduced to
powder, was slowly added while stirring with a magnet-
ic stirrer.
 INVESTIGATION AND TESTING TO DEVELOP AN INFILL FORMULA SUITABLE FOR OIL PAINTINGS ON COPPER

Table 3. in mixture could not be formed. However, when bees-

Microcrystalline waxes selected wax was melted with microcrystalline wax first then the
Laropal (either A 81 or A 101) was added, a mixture
Code Description Melting Range (ºC)
was easily achieved after 25 minutes. This demonstrated
KTW1 Techniwax 9211 84-88 that beeswax is a necessary ingredient when Larapol A
KTW2 Techniwax 9265 65 81 or 101 resin is used.
KTW3 Techniwax 9300 76 In contrast, achieving a mixture of each of the two
KTW4 Techniwax 9356 72-78 Regalrez resins with each of the five microcrystalline
KTW5 Techniwax 9426 72-78 waxes was very straightforward. All 10 different combi-
nations formed viable mixtures which took 17 to 40
minutes to prepare (Table 6). In addition, the 10 new
Table 4. formulations for WRs mixed very well with pigments
Synthetic resins selected and formed a uniformly coloured PWR with the pig-
ments remaining in suspension both in the liquid and
Code Description Melting Range (ºC)
solid phase.
L1 Laropal A 81 80-95
Table 6 also reports the acid number for the PWR
L2 Laropal A 101 95-110
reference samples and the new formulations. As expect-
R1 Regalrez 1094 95 ed, because of the presence of beeswax, the reference
R2 Regalrez 1126 124 samples proved to be acidic. Not surprisingly, the acid
number is higher for the WR formula with the highest
proportion of beeswax (C-PWR). The acid number for
all new formulations was zero.
As noted above, based on the colours available from
the C-PWR samples, titanium white and burnt umber
(Table 5) were chosen for all testing to allow a comparison
Properties of the new formulations
between the reference samples and the new formulations.
Melting ranges
While the McIntyre-Gamblin recipe called for 1:1 pig-
ment to wax-resin by weight, for the new formulations, a Melting range measurements of the 10 new formu-
similar consistency to the PWR references was achieved lations all showed a lower melting point than the pure
by adding titanium white and burnt umber in a ratio of products alone. This is in accordance with the literature
one part pigment to two parts wax-resin by weight. which reports a common phenomenon known as ‘Melt-
ing point depression’: the melting point of a mixture of
Results two different materials is never the average of the melt-
ing points of the two initial products, but is always low-
The first significant finding was that it was not pos- er than the melting point of the material present in the
sible to obtain a mixture of the microcrystalline waxes greatest amount (Isayev 2010).
chosen with either Laropal A 81 or A 101. After six However, it was also shown in this work that the
hours of mixing and several repetitions, a viable wax-res- resin with the highest melting point consistently affects

Table 5.
Pigments selected (from Kremer Pigmente)
Code Kremer pigment number Description Colour Index Chemical Description
P1 46200 Titanium White PW 6,7789 TiO2
Natural brown earth, con-
P2 40610 Burnt Umber, Cyprus PBr 8,7772
tains manganese oxides

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 DANIEL VEGA – ISABEL POMBO CARDOSO – LESLIE CARLYLE

Table 6.
Unpigmented WR reference samples compared with different combinations of microcrystalline waxes and Regalrez resins

Miscibility Time to Range of Workability

Wax-Resin Good Wor- Acid Num-
of compo- prepare Softening Melting Hardness
Codes kability ber
nents (minutes) Point (ºC) Point (ºC)
C-PWR 41 68 yes 16,056 2
G-PWR 42 69 yes 11,299 2
KTW1:R1 √ 25 41 70 yes 0 3
KTW1:R2 √ 40 43 73 yes 0 4
KTW2:R1 √ 17 25 50 no 0 1
KTW2:R2 √ 17 28 52 no 0 1
KTW3:R1 √ 21 24 50 no 0 1
KTW3:R2 √ 22 24 52 no 0 1
KTW4:R1 √ 18 39 57 no 0 1
KTW4:R2 √ 18 40 58 no 0 1
KTW5:R1 √ 22 41 64 yes 0 2
KTW5:R2 √ 25 41 68 yes 0 2
Hardness: 1. Soft; 2. Medium soft; 3. Medium hard; 4. Hard

Table 7. the overall melting point of the mixture by raising it one

Temperature range for reference PWRs and selected to three degrees Celsius more than when resin with the
WR formulations lower melting point was used (compare MPs for formu-
Tº Range for Workability las with R1 & R2 Table 6). As a result six of the new
Wax-Resin formulations were discarded as their melting range was
Pigment Softening Melting
Codes deemed to be too low (in fact, four of these formula-
Point (ºC) Point (ºC)
tions were very soft and tacky at room temperature).
C-PWR P1 42 69
Four formulations, KTW1-R1, KTW1-R2, KTW5-R1
P2 42 69 and KTW5-R2 were found to have melting ranges sim-
. P1 42 70 ilar to the WR reference samples. These consisted of
P2 42 70 microcrystalline waxes Techniwax 9211 (KTW1) or
KTW1:R1 P1 42 71 Techniwax 9426 (KTW5) with the resins Regalrez 1094
(R1) and Regalrez 1126 (R2).
P2 42 70
KTW1:R2 P1 43 74
It is important to note that the introduction of a
pigment was found to increase the melting point of the
P2 43 74
mixtures by one or two degrees Celsius (Table 7).
KTW5:R1 P1 42 66
P2 42 67
Workability and hardness
KTW5:R2 P1 42 69
Characteristics which were assessed empirically: work-
P2 42 70 ability and hardness, also revealed interesting results and
contributed to the choice of the final two formulations.
Regarding workability, both the PWR reference
samples and two of the remaining new formulations
were found to have the same application and working
parameters: the temperature required for softening was

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 INVESTIGATION AND TESTING TO DEVELOP AN INFILL FORMULA SUITABLE FOR OIL PAINTINGS ON COPPER
52ºC. Application was straightforward and efficient us-
ing the wax carving pencil; the PWRs were easily lev-
elled with gentle pressure while the infills were still
warm; and it was possible to work the infills at room
temperature by slight warming and to provide texture
using dental tools or a thin wooden stick.
The removal of excess material in the loss or around
its perimeter could be carried out mechanically or with
solvents. It was found that most of the excess PWR
could be gently removed with the point of a wooden
stick without causing damage to the paint surface. This
mechanical removal could then be followed by cleaning
with white spirit or with Shellsol D where necessary.
In addition, it was found that gloss, in the case of the
new formulations, like the PWR reference samples,
could be adjusted easily, and if required, a high gloss can
be achieved by buffing the surface with cotton wool or
soft fabric.
The new infills, like the PWR reference samples,
could be easily coated with a varnish based on Regalrez
1094 diluted in white Spirit (20g resin to 80 mls white
spirit). Nevertheless, since the infill material is sensitive
to most solvents and extensive brush application could
disrupt or remove the surface texturing, it may be pru-
dent to apply the varnish by spraying.
Hardness testing using a scalpel and a needle con-
firmed that the two new formulas chosen for their prop-
erties in workability were also the most similar to the
reference samples in terms of hardness. The two formu-
las chosen both consisted of four parts by weight of
Techniwax 9426 microcrystalline wax (code KTW5),
and one part of Regalrez: either Regalrez 1094 (R1) or
Reqalrez 1126 (R2). The dry pigment ratio for the new
formulations which best matched the PWR references
is one part pigment to two parts WR.
Stability of the new formulations
Reports on testing in the literature indicate that mi-
crocrystalline waxes (Rowe 2006; Gad 2008), and the
synthetic resins Regalrez 1094 and 1126 can be consid-
ered stable (Maines & de la Rie 2005). Preliminary
µFTIR and FTIR-ATR analyses of the new formulations
indicate that the materials are likely to remain stable since
spectra from the pure materials as well as the final mix-
tures show only the presence of saturated hydrocarbon
bonds (Appendix 3). These are known to be the least re-
active bonds found in organic compounds (Martel 2004).
In contrast, the spectra from the reference samples
C-PWR and G-PWR show the presence of functional
groups which are chemically more reactive. Of the func-
tional groups present, carbonyl groups are bonded to
esters, ketones and aldehydes. The esters are from the
beeswax present in both formulations. Ketones, present
in the C-PWR can be attributed to the polycyclohexa-
none resin used in its formulation, and the aldehydes,
present in the G-PWR sample, are associated with La-
ropal A 81. Also associated with the Larapol A 81 and
present in the G-PWR sample, are unsaturated bonds
and hydroxyl groups (Appendix 3).
Future research
Based on the µFTIR and FTIR-ATR results, it is
likely that the new formulations will prove to be more
chemically inert than the PWR reference samples.
However, it will be important to undertake photochem-
ical ageing tests of both the reference samples and the
new formulations with the individual materials alone
and in mixture (Ferreira et al. 2010). While the acid
number of the reference samples suggest that they will
promote corrosion on copper due to the beeswax they
contain, this has yet to be demonstrated.
It is also important to note that a recent study un-
dertaken of Laropal A 81 and Regalrez 1094, which
made use of different and more sensitive analytical in-
strumentation, provides new information about previ-
ously undetected features: in Laropal A 81 the presence
of polar groups, and in Regalrez 1094, of double bonds
(Bonaduce et al. 2013). In the later case further research
is required in relation to the use of Regalrez resins in
mixtures with microcrystalline wax.
Blooming is evident on both the C-PWR and the
G-PWR reference samples, however to date, it has not
been observed on the surfaces of the new PWR formula-
tions, nor was bloom observed by McIntyre on naturally
aged samples with microcrystalline wax alone (McIntyre
2011). Testing of the two new PWR formations for pos-
sible bloom development in ambient temperatures with
cycles of low and high relative humidity is planned.
Conclusions
The characterization of the PWR reference samples;
the Master thesis by Christine McIntyre; and the im-
portant suggestions made by Robert Gamblin regarding
147
 DANIEL VEGA – ISABEL POMBO CARDOSO – LESLIE CARLYLE
the preparation of the pigmented wax-resin mixture, all
formed the basis for these preliminary trials and testing
to explore and develop a new wax-resin formulation
suitable for infills on paintings with a copper substrate.
The reference samples from Carlyle and from Gam-
blin’s Pigmented Wax-Resin sticks proved to be very
important for guiding the choice of raw materials to be
used in the new formulation, and as anticipated, high-
lighted the potential problem of beeswax as an ingredi-
ent for infills on oil paintings with a copper substrate.
The characterization of the individual materials in the
new formulations made with Techniwax 9426 microcrys-
talline wax with Regalrez 1094 or 1126, suggest that
these new wax-resin mixtures with their acid number of
zero are likely to be chemically stable in relation to a cop-
per support. Since Regalrez 1094 has already been widely
adopted in the conservation field as a varnish for oil
paintings, and is therefore easily available, it is the most
likely candidate of the two Regalrez resins studied to be
used in the new PWR formula. However, as noted above,
further testing is required, especially on copper.
It is very encouraging that the working qualities of
the new formulations were found to be very similar to
the PWR reference samples. The newly formulated
PWR fills are easy to apply and achieve an excellent re-
sult regarding the infilling of very shallow losses. Fur-
thermore, their application temperatures and subse-
quent softening points were in the range suitable for use
on oil paintings.
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 INVESTIGATION AND TESTING TO DEVELOP AN INFILL FORMULA SUITABLE FOR OIL PAINTINGS ON COPPER

Figure 1a: Oil painting on copper, Virgin Mary, 17th century, private collection. 1b: detail of the paint losses showing the exposed copper
substrate. The paint composite (paint/ground layer) is in the range of c.30 µm which is similar to that found in a study of 12 17th & 18th
century oil paintings on copper (Vega 2015)

Appendix 1: Ingredient identification from
Tables 1 & 2
Commercial products:
The ingredients in the following commercial prod-
ucts were not identified by the authors at the time of
publication:
– Fine Surface Polly Filla; UVS Retouch Varnish;
Rowney Acrylic, Liquitex Acrylic Gesso, Modos-
tuc, Lefranc & Bourgeois Gel Relief, Lascaux Hy-
dro-Grund 750, Tempera paint.
Conservation products listed and identified in current lit-
erature/websites:
– Mowilith 20: Poly vinyl acetate resin based on low
molecular weight solid vinyl acetate homopolymer
[1]
– B-72: Paraloid B-72, Thermoplastic acrylic resin
based on a copolymer of ethyl methacrylate/methyl
acrylate (EMA/MA) in a ratio of 70:30 [2]
– B-48: Paraloid B-48, Thermoplastic acrylic resin
based on butyl acrylate/methyl methacrylate (BA/
MMA) copolymer (22-44%BA) [2]
– BTA: Benzotriazole; (C6H5N3), a nitrogen heterocy-
clic derivative [3]

151
 DANIEL VEGA – ISABEL POMBO CARDOSO – LESLIE CARLYLE

– Plextol B500: Acrylic dispersion [4] based on the
copolymer EA/MMA (66% EA) [2]
– Beva 371: Adhesive mixture based on the copoly-
mer ethylene/vinyl acetate. Original composition:
60% solvents: toluene and naphta with 40% solids:
two ethylene vinyl acetate copolymers (Elvax 150 re-
sin, and A-C Copolymer 400), cyclohexanone resin
(Ketone Resin N or Larapol K 80), a phthalate ester
of hydroabietyl alcohol (Cellolyn 21) and paraffin
wax. [5,6]. This product produced after 2010 con-
tains a substitute synthetic resin for the cyclohexa-
none resin and is referred to as Beva 371b [7]
References
Appendix 2: analytical instrumentation and
conditions
Fourier Transform Infrared Spectroscopy (μ-FTIR)
Infrared spectra were acquired using a Nicolet Nex-
us spectrophotometer coupled to a Continumm micro-
scope (15x objective) with a MCT-A detector cooled
by liquid nitrogen. The spectra were collected in trans-
mission mode, between 4000-650 cm-1, resolution set-
ting 4cm-1 and 128 scans, using a Thermo diamond
anvil compression cell. The spectra are shown here as
acquired, without corrections or any further manipula-
tions, except for the removal of the CO2 absorption at
ca. 2300-2400 cm-1.

[1] Kremer product information sheet for “Polyvinyl Acetate FTIR- Attenuated Total Reflectance (FTIR-ATR)
20”. Accessed 21 July 2016. Available at: <http://www. The FTIR analysis was performed using an Agilent
kremer-pigmente.com/media/pdf/67000e.pdf> 4300 Handheld FTIR Spectrometer with a diamond
[2] Down, J. 2015. ‘The evaluation of selected poly(vinyl ac- ATR head . Spectra were obtained covering the 4000-
etate) and acrylic adhesives: A final research update’, 650 cm-1 range, with spectral resolution of 4cm-1. The
Studies in Conservation 60(1): 33-54. collected spectra were obtained with 64 scans before
[3] Sease, C. 1978. ‘Benzotriazole: a review for conservators’, Fourier transform. Data was acquired by MicroLab®
Studies in Conservation 23(2): 76-85 software and data was matched by Polymers and Poly-
[4] Horie, C. V. 2010. Materials for Conservation: Organic mer Additives P/N 30002 ATR-FTIR Spectra database,
Consolidants, Adhesives and Coatings, 2nd ed. Oxford: from S.T. Japan (Europe Gmbh).
Butterworth-Heinemann
[5] Ploeger, R., De la Rie, E., McGlinchey, C., Palmer, M.,
Maines, C.A., Chiantore, O. 2014. ‘The long-term sta-
bility of a popular heat-seal adhesive for the conservation
of painted cultural objects. Polymer degradation and sta-
bility’, Polymer Degradation and Stability (107):307-313
[6] McGlinchey, C. Ploeger, R., Colombo, A., Simonutti, R.
Palmer, M. Chiantore, O. Proctor, R., Lavédrine, B., De
la Rie, E. 2011. ‘Lining and Consolidations Adhesives:
Some new developments and areas of future research’. Pa-
per present at the Proceeding of Symposium 2011 – Ad-
hesives and Consolidants for Conservation: Research and
Applications. October 17-21 October. Canada: Ottawa
[7] Beva reformulated formula. Accessed 23 October 2016.
Available at: <http://www.conservationsupportsystems.
com/system/assets/msds/New_Beva_Formula>

152
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Appendix 3: FTIR analysis

Figure A-1 – μ-FTIR-ATR spectrum of the wax-resin KTW5:R2 and of the pure materials: microcrystalline
Techniwax 9426 (KTW5) and Regalrez 1126 (R2). Spectra show the presence of hydrocarbon bonds only.

C-PWR

Figure A-2- μ-FTIR spectrum of the unpigmented wax-resin from Carlyle (C-PWR) with reference spectra of
beeswax and of cyclohexanone resin. The spectra show the presence of carbonyl groups associated to ketones (in poly
cyclohexanone) and esters (in beeswax).

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 DANIEL VEGA – ISABEL POMBO CARDOSO – LESLIE CARLYLE

G-PWR

Figure A-3- μ-FTIR spectra from Gamblin Pigmented Wax Resin Stick, Neutral Base G-PWR and
reference spectra of beeswax, a spectra of the microcrystalline wax Techniwax 9426 (KTW5) for
comparison and a reference spectra of Laropal A 81. Spectra show the presence of carbonyl groups
associated with aldhydes (in Laropal A 81) and esters (in beeswax); as well as unsaturated bonds (in
Laropal A 81).

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 INVESTIGATION AND TESTING TO DEVELOP AN INFILL FORMULA SUITABLE FOR OIL PAINTINGS ON COPPER

Appendix 4: Equipment and suppliers
Equipment
– Digital precision balance: Precisa®, model 500M
2000C
– Magnetic Stirrer with Heating: Heidolph®, model
MR Hei-Standard. This laboratory device employs a
rotating magnetic field to cause a stir bar immersed
in a liquid (contained in a glass vessel) to spin under
controlled speed, making the process of obtaining
an homogeneous mixtures more efficient.
– Wax carving pencil: This unit was originally designed
to carve and mould a variety of waxes used in the
dental industry. The variety of carving tips and easy
temperature control allow for precise waxing work.
Temperature range is between 50 to 200ºC. For using
with PWR, it is available through Gamblin (www.
gamblincolors.com/conservation-colors/)

MATERIAL
SUPPLIER DATE RECEIVED
(PROJECT CODE IN BRACKETS)
Techniwax samples:
9211 (KTW1)
Kerax®
9265 (KTW2)
Received 2015
9300 (KTW3)
www.kerax.co.uk
9356 (KTW4)
9426 (KTW5)
Gamblin Pigmented Wax Resin sticks (G-PWR) Gamblin Conservation Colours
www.gamblincolors.com/conserva- 2009 and 2015
tion-colors
Regalrez® 1094 (R1)
Regalrez® 1126 (R2) Kremer Pigmente GmbH & Co.
2015
Laropal® A 81 (L1) KG
Laropal® A 110 (L2)
Paintings laboratory supplies
Pigments: Titanium White and Burnt Umber www.kremer-pigmente.de
ParaloidTM B-72
Potassium hydroride
BioXtra, >85% KOOH basis (P5958 FLUKA)
FCT-Scientific lab
Hydrochloric acid
ACS reagent, 37% (320331 FLUKA) Sigma-Aldrich
Phenolphthalein www.sigmaaldrich.com
ACS reagent (105945)
96% ethanol FCT-PhotoChemistry Lab
Puriss. P.a., ACS reagent, reag. Ph. Eur., 96%
(v/v) (32294 RIEDEL-DE HAËN)
Xylene
Paintings laboratory supplies
Reagent grade (214736 ALDRICH)
Fine sable-haired brush
Winsor & Newton Paintings laboratory supplies
Cotman Watercolour Round III Series

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 DANIEL VEGA – ISABEL POMBO CARDOSO – LESLIE CARLYLE
Appendix 5: Standard Test Method for Acid
Number (empirical) of synthetic and natural
waxes
The standard D13865, published by the American
Society of the Association for Testing and Materials
(ASTM), was followed for this test. Information from
the standard has been extracted here:
Scope:
– This test method covers the determination of the acid
number of synthetic waxes and natural waxes. The
number is obtained by direct titration of the material
and indicates the amount of free acid resent.
– This test method, using an ethanol-xylene mixture,
is applicable to all natural waxes, including carnau-
ba. The test method is also applicable to oxidized
microcrystalline waxes, oxidized Fischer-Tropsch,
oxidized polyethylene, and montan esters.
– The values stated in SI units are to be regarded as
standard. No other units of measurement are in-
cluded in this standard.
Significance and use
This test method is used to determine the property
of acid functionality. Acid functionality determines the
utility of the wax as well as being a significant Quality
Control test.
Reagents and materials
– Purity of Reagents: Reagent-grade chemicals or
equivalent, as specified in Practice E200, shall be use
in all tests.
– Ethanoic Potassium Hydroxide, Standard Solu-
tion: Dissolve approximately 5.6 g of potassium hy-
droxide in 5.6 g of distilled water. Dilute with USS-
D3A denatured ethanol or 95% ethanol to 1000
mL. Standarize with 0.1 N hydrochloric acid.
– Phenolphthalein Indicator Solution (10 g/litre):
Dissolve 1 g of phenolphthalein in 100 mL of USS-
D3A, denatured ethanol or 95% ethanol.
– Xylene
Procedure
1. Transfer1 to 2 g of the sample, weighed to the near-
est 0.001 g to a 250-mL acid-value flask. Add 40 mL
156
of xylene. Heat on a hot plate or water bath to put
the sample into solution. Occasional swirling may
be necessary.
2. Add 3 to 5 drops of phenolphthalein indicator solu-
tion and titrate the hot solution to the first persistent
pink colour. The end point is taken when the pink
colour remains for at least 10s. Swirl the flask vigor-
ously during the titration. If precipitation of waxes
occurs during titration, reheat the sample. The ti-
tration should be carried out as quickly as possible.
Record the number of millilitres of standard alkali
solution used. Warning - to avoid saponification, do
not reheat the solution during this operation.
3. Determine the blank titration value by repeating the
procedure without the addition of sample material.
4. Run a total of three titrations of sample being tested
and one blank.
Calculation
Calculate the acid number as follows:
Acid number = (A – B) x N x (56.1)/C
A = millilitres of alkali solution required for titration
of the sample,
B = millilitres of alkali solution required for titration
of the blank sample,
N = normality of the alkali solution, and
C = grams of sample used.
Notes
1. [1] Dr Bartl, at The Institute of Chemical Technology (Prague),
has studied bloom development on beeswax in natural ageing
conditions by storing samples at 4ºC for a minimum of 3 years
(2015, 2013, 2008).
2. Personal communication Dr Carlyle, 2015. Barbara Klempan in-
troduced a PWR formula to paintings conservators at CCI after
her training in Copenhagen.
3. Robert Gamblin kindly shared this information with the authors
to assist in the current study.
4. These fragments, 224 x 38 mm and 430 x 50 mm respectively,
were donated from a private collection for study (Vega 2016).
5. The edition used was approved and published in October 2015.
Originally approved in 1955 as D1386-55T. The most recent
previous approved standard was published in 2010 as D1386.