Journal of the American Institute for Conservation

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Effect of residual sulfur content on the

degradation behavior of cellulose acetate

Catherine H. Stephens

To cite this article: Catherine H. Stephens (2018): Effect of residual sulfur content on the
degradation behavior of cellulose acetate, Journal of the American Institute for Conservation, DOI:
10.1080/01971360.2018.1535029

To link to this article: https://doi.org/10.1080/01971360.2018.1535029

Published online: 08 Nov 2018.

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JOURNAL OF THE AMERICAN INSTITUTE FOR CONSERVATION
https://doi.org/10.1080/01971360.2018.1535029

Effect of residual sulfur content on the degradation behavior of cellulose acetate

a,b
Catherine H. Stephens
a
Department of Scientific Research, Metropolitan Museum of Art, New York, NY, USA; bInstitute for the Preservation of Cultural Heritage (IPCH),
Yale University, New Haven, CT, USA

ABSTRACT KEYWORDS
Four unplasticized, commercially available cellulose acetate (CA) powders were artificially aged for Sulfate groups; cellulose
up to 30 weeks in a humid oven at 70°C and 50% relative humidity (RH) to see if higher levels of acetate; degradation;
residual sulfate groups (−OSO2OH)− attached to the cellulose backbone affected degradation. artificial aging
Qualitative x-ray fluorescence (XRF) of unaged powders showed that three contained the same
amount of sulfur while the fourth exhibited more. Three powders were manufactured recently
whereas the fourth was produced in the 1970s. Powders were aged in lidded borosilicate glass
bottles to impede evaporation of acids generated during artificial aging. A water reservoir was
enclosed within each bottle to help maintain humidity. Changes to the level of acidity and
sample weight were characterized at various time points. All samples emitted acid vapor with
aging yet the powder with higher residual sulfate content emitted the most. Similarly, with
aging, only the powder with higher level of sulfur content showed a weight loss. No unique
behavior was observed from the powder that had naturally aged for forty years before being
artificially aged.

RÉSUMÉ
Quatre acétates de cellulose en poudre sans plastifiant ajouté, vendus dans le commerce, ont été
artificiellement vieillis pour une durée allant jusqu’à trente semaines dans une enceinte humide à
70°C et 50% d’humidité relative pour démontrer que des niveaux plus élevés de groupes sulfates
(-OSO2OH-) résiduels, attachés à la chaîne de cellulose, en affectait la dégradation. L’analyse
qualitative par spectroscopie de fluorescence des rayons X des poudres non vieillies a montré
que trois des acétates de cellulose contenaient la même quantité de groupes sulfure, alors que
le quatrième en contenait plus. Les trois premières poudres sont produites récemment alors que
la quatrième a été produite dans les années 1970. Les poudres ont été âgées dans des flacons
en verre borosilicate avec couvercle, pour éviter l’évaporation des acides produits pendant le
vieillissement artificiel. Un réservoir d’eau était également placé dans chaque flacon pour
maintenir le niveau d’humidité. Les variations d’acidité et de poids des échantillons ont été
mesurées plusieurs fois au cours du vieillissement. Tous les échantillons ont émis des vapeurs
acides durant leur vieillissement, mais la poudre contenant le plus de sulfate résiduel en a émis
le plus. De même, au cours du vieillissement, seuls les échantillons de la poudre dont le niveau
de sulfures était plus élevé ont subi une perte de poids. Il n’a pas été observé de comportement
particulier pour la poudre qui avait vieilli naturellement pendant quarante ans avant d’être
artificiellement vieillie. Traduit par Claire Cuyaubere.

RESUMO
Quatro talcos de Acetato de Celulose (CA) não plastificados, disponíveis comercialmente, foram
envelhecidos artificialmente por até 30 semanas em um forno úmido a 70°C e 50% de Umidade
Relativa (UR) para verificar se níveis mais altos de grupos de sulfato residuais (−OSO2OH)−
ligados à cadeia principal de celulose afetaram a degradação. A Fluorescência de Raios X
qualitativa (XRF) de talcos não envelhecidos mostrou que três deles continham a mesma
quantidade de grupos de enxofre enquanto o quarto exibia mais. Três talcos foram fabricados
recentemente enquanto o quarto foi produzido nos anos 1970. Os talcos foram envelhecidos em
garrafas de vidro borosilicato com tampa para impedir a evaporação de ácidos gerados durante
o envelhecimento artificial. Um reservatório de água foi também colocado dentro da garrafa
para ajudar a manter a umidade. Mudanças no nível de acidez e peso da amostra foram
caracterizadas em vários momentos. Todas as amostras emitiram vapor ácido com o
envelhecimento, embora o talco com maior teor residual de enxofre tenha emitido mais. Da
mesma forma, com o envelhecimento, apenas o talco com maior teor de enxofre apresentou
perda de peso. Nenhum comportamento singular foi observado no talco que envelheceu
naturalmente por quarenta anos antes de ser artificialmente envelhecido. Traduzido por Sandra
Baruki.

CONTACT Catherine H. Stephens catherine.stephens@metmuseum.org Department of Scientific Research, Metropolitan Museum of Art, 1000 Fifth
Avenue, New York, NY 10028, USA; Institute for the Preservation of Cultural Heritage (IPCH), Yale University, New Haven, CT 06516, USA
© American Institute for Conservation of Historic and Artistic Works 2018
2 C. H. STEPHENS

RESUMEN
Cuatro polvos de acetato de celulosa (AC) no plastificados, comercialmente disponibles fueron
envejecidos artificialmente por hasta 30 semanas en un horno húmedo a 70°C and 50% de
humedad relativa (HR) para ver si niveles más altos de grupos de sulfatos residuales
(−OSO2OH)− unidos a la columna vertebral de la celulosa afectaban la degradación. La
fluorescencia de rayos-x cualitativa (FRX) de los polvos sin envejecer mostró que tres de ellos
contenían la misma cantidad de grupos de azufre mientras que el cuarto presentaba más. Tres
polvos fueron fabricados recientemente, mientras que el cuarto fue producido en la década de
1970. Los polvos fueron envejecidos en botellas de vidrio de borosilicato con tapa para impedir
la evaporación de los ácidos generados durante el envejecimiento artificial. También fue incluido
un depósito de agua dentro de cada botella para ayudar a mantener la humedad. Los cambios
en el nivel de acidez y el peso de la muestra fueron determinados en varios puntos a lo largo
del tiempo. Todas las muestras emitieron vapor de ácido con el envejecimiento, pero el polvo
con mayor contenido de sulfato residual fue el que más emitió. De manera similar, con el
envejecimiento, solo el polvo con mayor nivel de contenido de azufre mostró una pérdida de
peso. Ningún comportamiento particular fue observado en el polvo que había envejecido
naturalmente durante cuarenta años antes de ser envejecido artificialmente. Traducido por
Andrea Venosa ; revisado por Amparo Rueda.

what happens if either becomes consumed, or if either

Introduction
When cellulose is converted to cellulose acetate (CA)
using the solution process, sulfuric acid is most fre-
quently used as the catalyst (Malm and Hiatt 1954).
Using this method, hydroxyl groups on the cellulose
chain are initially replaced with sulfate groups that, fol-
lowing the addition of acetic anhydride to the mixture,
later are replaced by acetyl groups. When the acetylation
process is stopped by the addition of dilute aqueous
acetic acid to the mixture, small quantities of residual
sulfate groups remain attached to the cellulose chain
(up to 0.5% in the final solution) as the reaction does
not go to 100% completion (Hiatt and Rebel 1971). It
has been known, since as early as the 1920s, (Mork
1926) that these attached residual sulfates lead to chemi-
cal instability (Keirstead and Myers 1954; Malm et al.
1964; Malm and Hiatt 1954; Stannett 1950). With time,
the sulfate groups are hydrolyzed from the cellulose
chain, forming very reactive acid groups, more so than
the acetyl groups that are also famously hydrolyzed
during CA degradation. Neutralizers such as magnesium
carbonate, magnesium acetate, or sodium acetate, and
stabilizers, in the form of antioxidants and UV absorbers
(Wilson and Forshee 1959), are typically added during
processing to neutralize any lingering free sulfuric acid
or sulfates that hydrolyze during aging or exposure to
heat and humidity (Hiatt and Rebel 1971).
While the reaction chemistry and processing of CA is
well known, the role residual sulfate groups play in the
long-term natural-aging behavior of CA seems less so.
Save for some decades-old patent applications (Malm
and Williams 1954; William and Lowe 1959), no pub-
lished literature was located by the author that outlined
precisely how much neutralizer or stabilizer is added,
exclusively neutralizes sulfate groups, as both sulfate
and acetate groups are eventually formed during
hydrolysis of CA. The literature does, however, discuss
CA degradation in terms of deacetylation, a bigger
concern due to the acetyl group concentration in the
polymer (up to 44.8%) (Evans and McBurney 1949;
Rambaldi et al. 2014; Vos, Burris, and Riley 1966).
Recently, two research projects used ion chromato-
graphy to observe sulfates found in naturally-aged CA
artifacts (Ballany et al. 2001; Littlejohn et al. 2013).
However, those samples also contained plasticizers;
historic artifacts were sometimes plasticized with sulfur-
containing compounds such as p-toluene-sulfonamide,
N-ethyl-p-toluenesulfonamide, or N, N-diethylsulfona-
mide (Stannett 1950; Private communications with Joy
Mazurek). Hence, while the data was reliable, it was
unclear whether the sulfates came from the CA or from
an additive. While the role the sulfates played in the overall
degradation scheme was not discussed, one way to
improve the experiment would have been to remove any
potential contribution from plasticizers by dissolving the
sample in a solvent and then precipitating it in a non-sol-
vent before performing other analyses.
This communication endeavors to demonstrate that
even if the CA was recently produced and is free from
colorants, plasticizers, or other additives, it is a hazard
to itself. While no new ground is sown here (almost
100 years ago it was known that residual sulfates pose
a stability problem), the goal of this work was to high-
light that higher levels of residual sulfate content may
accelerate degradation; if true, conservators and
museums should be alerted in order to consider new
ways of classifying and treating CA-based artifacts. For
instance, it may be that only higher sulfate content

materials require cold storage, or perhaps the life of CA
artifacts could be extended by developing treatments
focused on addressing the sulfate content. To that end,
the following characterization methods were carried
out in an attempt to highlight this effect: x-ray fluor-
escence as well as changes to off-gassing acids and pow-
der weight with aging.
Experimental
Four CA powders were used during the course of this
study. The first was definitively manufactured by East-
man Kodak and dates to the 1970s (CA1). It was
included in the study to compare with the aging of two
recently manufactured powders, i.e, would a roughly
forty-year-old sample degrade differently from two con-
temporary ones. The two samples were purchased from
Sigma-Aldrich, one with a number average molecular
weight of 30,000 (CA2), the other with 50,000 (CA3).
Though Sigma Aldrich would not reveal the manufac-
turer of the products they were distributing, it is pro-
posed here that both CA2 and CA3 were manufactured
by Eastman Chemical (Eastman) as they have the same
properties of two products available from Eastman
(CA2 correlates with catalog number CA-398-6 and
CA3 correlates with catalog number CA-398-10).
These three powders share a degree of substitution
(DS) around 2.45, which is appropriate for cellulose acet-
ates used in making film and plastics (Hon 1997). The
last sample was purchased from Fluka Analytical
(CA4); with a very low DS, it would likely be inappropri-
ate for use in making films yet was useful as a sample in
this study as it contained a unique residual sulfate con-
tent. The properties of these materials as provided by
the distributors are given in Table 1.
Before aging, a Bruker Tracer handheld x-ray fluor-
escence spectrometer (XRF) was used to qualitatively
detect the elemental composition of each CA. Data
were collected with the vacuum pump on, at 15 KV, 20
μA, and for 120 seconds and samples were prepared
for this analysis in accordance with ASTM standard
test method D2929-89, Standard test method for sulfur
content of cellulosic materials by x-ray fluorescence. As
Table 1. Properties of the four cellulose acetate powders
examined in this study as provided by the distributor.
Molecular
Degree of weight
Name Distributor substitution (DS) (Mn)(g/mol)
CA1 Eastman Kodak 2.47
CA2 Sigma-Aldrich 2.45 30,000
CA3 Sigma-Aldrich 2.45 50,000
CA4 Fluka Analytical 1.0
JOURNAL OF THE AMERICAN INSTITUTE FOR CONSERVATION 3
the method was qualitative, no standard samples were
used to generate a calibration curve.
For the artificial-aging component of this study, pow-
ders were pre-conditioned for three days at 23°C and
50% relative humidity (RH) in a Harris Environmental
Systems constant environment chamber. Following
that, 6.0 g of powder was measured out then poured
into a 35 mL borosilicate weighing bottle. In a separate
borosilicate glass vial, 1 mL of water was also inserted
into the bottle before placing the lid on top. The water
was added in an attempt to maintain a constant humidity
inside the weighing bottle during aging. Forty four
samples were prepared, with one bottle made for each
time point and 11 bottles prepared per CA powder.
Forty samples were put in a Blue M temperature/
humidity test chamber and aged up to 30 weeks at 70°
C and 50% RH. The remaining four bottles, one of
each powder, were set aside and identified as “0”, i.e.,
an unaged control. One bottle of each sample was
removed at 7, 16, 28, 43, 63, 84, 105, 126, 168, and 210
days of artificial-aging. When samples were removed
from the oven, the lid was removed, an A–D strip
(Image Permanence Institute) was added to the bottle,
and the lid was quickly replaced. After sitting for three
weeks at ambient conditions, the A–D strips were
removed from vials and photographed while the weight
of each powder was recorded by pouring it out into a
tared weighing boat. Minimal powder was lost during
the weighing process.
Results and discussion
The XRF data of the four unaged CAs is seen in Figure 1.
The CA4 showed the highest residual sulfur (S) (Kα =
2.31) content while the other three CA powders showed
lower, but equivalent, amounts of S. Since these samples
were unplasticized, and powders were prepared, in
accordance with the ASTM method, to remove any evi-
dence of non-combined sulfur compounds, the S peak
was ascribed to residual sulfate groups attached to the
CA chain. Hence, the CA4 powder had the highest
residual sulfate content.
All four samples also contained equal yet small
amounts of aluminum (Al) (Kα = 1.48), silicon (Si)
(Kα = 1.74), phosphorous (P) (Kα = 2.01), iron (Fe)
(Kα = 6.40), and nickel (Ni) (Kα = 7.48) as well as cal-
cium (Ca) (Kα = 3.69) in varying amounts. As these
four powders were proprietary materials, it was not poss-
ible to know exactly why these elements were present.
Date purchased
However, Al and P are sometimes added during syn-
1970s
2015 thesis as stabilizers (Ahluwalia, Fisch, and Peveler
2015 1991; Haney 1937; Kiefer and Touey 1959). It was not
2015
known why Ca was observed in CA2 and CA4 but not
4 C. H. STEPHENS
Figure 1. X-ray fluorescence spectra of unaged cellulose acetate powders used in this study.
CA1 or CA3 although Ca has been shown to be added to
aid the acetylation process (Salamone 1996). As for the
Si, Fe, and Ni, it was not known why they were present.
Previously, Littlejohn et al. (2013) noted that Fe was
found in cellulose acetate artifacts but ascribed its pres-
ence to pigments added to the artifacts to give them
color; that wouldn’t be the case here as the powders
weren’t colored. All three are components of steel and
perhaps are impurities from manufacturing.
After the elemental content of the controls was deter-
mined, samples were artificially-aged. Figure 2 shows a
photograph of the four powders before (“0”) and after
7 and 70 days of aging. Powders CA1, CA2, and CA3
all remained relatively white with aging. In addition,
when tipped or shaken in a container, the three powders
flowed easily. By contrast, the CA4 sample had a slightly
creamy color before aging that became darker and more
yellow with aging. Also, the CA4 particles stuck together
and didn’t flow if the container was agitated. It was
Figure 2. Photograph comparing the color changes to the four cellulose acetate powders before aging (0), and at 7 days (7) and 70 days
(70) of aging at 70°C and 50% RH.
inferred from the coloring and physical behavior of
CA4 that some form of chemical degradation had
occurred as cellulose-based materials are known to yel-
low upon aging (Stephens et al. 2008).
Aged samples were examined for evidence of evapor-
ating acid by analyzing color changes to bromocresol
green containing A–D strips that were placed in each
sample bottle after removal from the humid oven. As
the strips changed from blue, indicating a pH of 5.4, to
yellow, indicating a pH of 3.8, it was possible to infer
the level of chemical damage, in the form of hydrolysis
of acetic acid and sulfuric acid groups, as a function of
artificial-aging. Figure 3 shows A–D strips from all
four powders for all time points, with results from CA1
on the top, and CA2, CA3, and CA4, consecutively,
underneath. Three of the four images (CA1, CA2, and
CA3) show a pencil with four different colors on them,
which is provided by the manufacturer to assess damage
from gaseous acids.

Figure 3. Change in color of A–D strip when placed in contact with cellulose acetate powders artificially-aged at 70°C and 50% RH in an
enclosed borosilicate bottle.
In general, strips developed their final color within the
first five days of being placed in a bottle. The sample
showing the least amount of color change to the A–D
strips with time was CA3. The sample that showed the
greatest amount of color change to the strip and hence
acid generation was CA4. Two conclusions might be
drawn from this result: one, that more sulfate and acetate
groups were hydrolyzed in the CA4 sample, lowering the
pH of the environment and catalyzing further degra-
dation. An alternate conclusion to these observations
could be that the CA4 degraded faster because it had a
lower starting degree of substitution (DS), as was con-
cluded in another study (Samios, Dart, and Dawkins
1997). A way to clarify the issue would be to synthesize
JOURNAL OF THE AMERICAN INSTITUTE FOR CONSERVATION 5
two CAs with the same DS but different residual sulfate
contents and perform the same study.
Powders were also weighed after aging. Previous
workers who aged plasticized CA samples under the
similar conditions observed significant changes to the
weights of their samples with time and ascribed the
decrease to plasticizer and acetic acid loss (Ballany
et al. 2001). Results in this study differed slightly as
there was no plasticizer present; hence, any weight
changes were from moisture uptake or release, or acetic
acid and sulfuric acid loss. Figure 4 shows that at short
aging times, the weight of all four CA powders increased.
This was because the water in the vials inside the borosi-
licate bottles volatilized and was absorbed by the
6 C. H. STEPHENS
Figure 4. Change in sample weight of cellulose acetate powders artificial-aged at 70°C and 50% RH in an enclosed borosilicate bottle.
hygroscopic CA. The adsorbed water increased the
weight of the powders.
With prolonged aging, samples CA1, CA2, and CA3
showed a decrease, then leveling off in the weight
measured in each bottle. While the increase at early
times was ascribed to an uptake of moisture by the
hygroscopic CA, the decrease at later times was ascribed
to the onset of deacetylation and desulfation as seen in
the A–D strips. By contrast, the weight of CA4 powders
began to decrease below the original 6.0 g starting at
about 105 days of aging, implying that more deacetyla-
tion and desulfation had occurred in this sample than
observed in the other three.
Taking into account that at ambient humidity, the orig-
inal mass of the powder was 6.0 g and at the end of the
experiment it weighed 5.4 g, the CA4 sample experienced
a 10 wt. % loss during artificial-aging. If the monomer
molecular weight of a CA with a DS = 1 is 204 g/mol, it
was approximated that the CA4 sample lost up to half
of its acetyl groups during the course of the experiment.
Since the calculation does not take into account the loss
of sulfate groups, the acetyl group loss would be slightly
less than the theoretical value. The other three CA samples
lost markedly fewer acetyl groups.
Conclusions
The goal of this communication was to examine the
effect of residual sulfate groups on the aging behavior
of four unplasticized cellulose acetate powders. While
three of the four commercial powder samples examined
showed similar sulfur content, the sample containing
more sulfate groups, CA4, degraded in a manner unique
to the other three. It emitted more acids and lost more
weight during artificial-aging than the other three. It is
proposed that the higher residual sulfate content was at
least partially responsible for these outcomes. More
work, in the form of controlled synthesis of CAs with
similar degrees of substitution but differing residual sul-
fate content, followed by size exclusion chromatography,
to see if any of the changes observed were due to main
chain degradation, in concert with the tests performed
above, will be necessary to separate the effect of residual
sulfate content from the degree of substitution on the
overall degradation rate.
The conclusion proposed here, that cellulose acetate
molecules with more residual sulfate groups are less
thermally stable and more readily degraded than those
with less, is not novel. Over the course of several dec-
ades, from the 1940s to 1960s, Dr. Carl J. Malm, a scien-
tist at the Eastman Kodak Company, researched and
published on this specific subject; his work optimized
the manufacturing process in order to minimize the
amount of residual sulfates in cellulose acetate. This
article aspired to alert the conservation community of
this information by conducting some simple exper-
iments that hint that this is the case and to propose
that one reason, amongst several, some cellulose acetates

in museum collections maintain their shape and appear-
ance while others shrivel, discolor, or break, is due to
differences in residual sulfate content. Two possible
future projects are seen from this work: a non-invasive
XRF survey of CA in collections to compare the sulfur
content against the condition of the object. If it turns
out that there is a relationship between sulfur content
and condition, it may be that the sulfate content could
be used as a way to classify which objects are more in
need of freezer storage vis-à-vis other objects. A second
project would entail developing a conservation treat-
ment that either inhibits sulfate group hydrolysis or
that scavenges and neutralizes sulfates in the event
they do hydrolyze as sulfuric acid is more reactive
than acetic acid.
Acknowledgements
This work was performed under an operating grant provided
by the Andrew W. Mellon Foundation. Dr. Odile Madden
and Professor Kevin Edgar are acknowledged for discussions
during the inception of this work.
Disclosure statement
No potential conflict of interest was reported by the author.
Funding
This work was supported by The Andrew W. Mellon Foun-
dation [grant number 41100638].
Notes on contributor
Dr Catherine H. Stephens has worked at The Metropolitan
Museum of Art for two and a half years. Prior to that, she
worked at the Institute for the Preservation of Cultural Heri-
tage, Yale University, in the Aging Diagnostics Lab; this lab
was previously known as the Art Conservation Research Cen-
ter and was located at Carnegie Mellon University. Catherine
holds a Ph.D. in macromolecular science and engineering
from Case Western Reserve University and BA degrees in
both chemistry and art history from SUNY College at Geneseo.
Her current position is focused on studying volatile organic
compounds that are hazardous to cultural heritage. Previously,
her specialty was studying the degradation mechanisms
and structure-property relationships of polymeric materials
found in museums.
ORCID
Catherine H. Stephens http://orcid.org/0000-0001-8225-
3092
JOURNAL OF THE AMERICAN INSTITUTE FOR CONSERVATION 7
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