Adhesive Testing at The Canadian Conservation

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Adhesive Testing at the Canadian Conservation Institute: An Evaluation of Selected Poly(Vinyl
Acetate) and Acrylic Adhesives
Author(s): Jane L. Down, Maureen A. MacDonald, Jean Ttreault and R. Scott Williams
Source: Studies in Conservation, Vol. 41, No. 1 (1996), pp. 19-44
Published by: on behalf of the Maney Publishing International Institute for Conservation of
Historic and Artistic Works
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ADHESIVE TESTING AT THE CANADIAN CONSERVATION
INSTI' I' UTE AN EVALUATION OF SELECTED
POLY(VINYL
ACETATE)
AND ACRYLIC ADHESIVES
Jane L.
Down,
Maureen A.
MacDonald,
Jean Tetreault and
R. Scott Williams
Summary-In
1983 the Canadian Conservation Institute
(CCI)
initiated a
project
to evaluate 27
poly(vinyl
acetate) (PVAC)
and 25
acrylic
adhesives on the basis
of pH, emission
of harmful volatiles,
flexibility/
strength
and
yellowing upon
dark
aging
at room
temperature
and
fluorescent light aging.
Measurement
of
the
pH of
extracts showed that the PVAC adhesives were more acidic than the
acrylic
adhesives and that
light
aging
tended to decrease the
pH of
both classes. The PVAC
homopolymers generally
were more acidic than
the PVAC
copolymers
and
many acrylic
adhesives
containing butyl acrylate
were
found
to be neutral. The
analysis of
volatile
compounds from
the PVAC and
acrylic
adhesives showed that
they
emitted various ester
and residual solvent
compounds
but
only
the PVAC adhesives released
appreciable
quantities of
acetic acid.
The results indicated
that,
after
an initial
curing period of
several
weeks, the evolution
of
acetic
acidfrom
the
PVAC adhesives should not
pose
an acute hazard. In
general,
both PVAC and
acrylic
adhesives became less
flexible
after
dark
aging
and the PVAC adhesives
possessed
more
strength
and less
flexibility
than the
acrylics.
PVAC
copolymers displayed
and retained more
flexibility
than PVAC
homopolymers.
The PVAC
adhesives
yellowed approximately
twice as
quickly
as the
acrylic
adhesives and
light aging
tended to make all
the adhesives
yellow
more
quickly
than dark
aging.
The results
of
each test
for
each adhesive are tabulated
for
an overall view and assessment
of
the data.
Introduction
In 1983 the Canadian Conservation Institute
(CCI)
initiated a
project
to evaluate various
poly(vinyl
acetate) (PVAC)
and
acrylic
adhesives. The
project
was outlined in a
paper given
at the IIC Paris
Congress
in 1984
[1].
The
purpose
of the
project
was to test certain
properties
of selected PVAC and
acrylic
adhesives
upon aging.
The
properties
moni-
tored were
pH,
emission of harmful
volatiles,
flexi-
bility, strength
and
yellowing.
Some of the results
(pH
and
volatiles)
have been
published
elsewhere
[2]
and all of the results have been made available
in an internal
report
[3]. The
pH and volatile emis-
sion results are
repeated
here with more recent
data, along
with new information on
flexibility,
strength
and
yellowing.
All of the results are exam-
ined
together and,
based on
this,
the most stable
adhesives were identified.
Selecting
PVAC and
acrylic
adhesives for
testing
One hundred and seven PVAC and 49
acrylic
adhe-
sives were
proposed by conservators,
conservation
supply
houses and manufacturers for inclusion in
Received 20 December 1994
Received in revised
form
November 1995
this
study.
Since it was
impossible
to test all 156
adhesives,
a
screening procedure [2]
based on chem-
ical
composition
of the
major components
was
introduced to reduce the numbers while
keeping
a
representative sample.
Simple, quick,
batch methods of
analysis
were
used to sort the adhesives into chemical
groups.
Fourier transform infrared
(FTIR) spectroscopy
was the
primary technique employed.
Some addi-
tional information was obtained from colour
spot
tests
(presence
of
dextrin,
cellulose
nitrate, etc.),
the
Beilstein test for chlorine
(presence
of
poly(vinyl
chloride))
and
X-ray microanalysis (presence
of
inorganic
fillers such as
talc,
china
clay, etc.).
These
methods were sufficient for the
purpose
of
screening
according
to the
composition
of
major components.
Minor
components
and molecular
weights
were not
determined.
FTIR
spectra
were obtained from thin films cast
on silver chloride
plates.
The casts were made from
the solutions or
dispersions
as
received,
or from
tetrahydrofuran,
ethanol or toluene
(methylben-
zene)
solutions of solid
products.
Spectra
of the
samples
cast as received were use-
ful for
determining
the
general
nature of the adhe-
sive.
However, especially
for
PVACs,
little
discrimination between
products
could be made
from these
spectra
because
they
were dominated
by
Studies in Conservation 41
(1996)
19-44
19
J.L.
Down,
M.A.
MacDonald, J. Tetreault and R.S. Williams
Table 1
Summary of
the results
of
the
analyses of
the
poly(vinyl acetate) adhesivesfor
adhesive selection
Vinyl acetate
homopolymers
No additives
VAL/VAC
Cellulose nitrate
Multiwax #445
VAL/VAC +
soap
VAL/VAC + PH
VAL/VAC + TS
Soap
+ dextrin
PVP + PH
VAL/VAC +
soap
+
polyamide
VAL/VAC +
soap
+ PEGD
VAL/VAC +
soap
+ PH
VAL/AC +
soap
+ UN1
VAL/VAC +
soap
+ UN2
VAL/VAC +
dye
+
polyamide
VAL/VAC + NaCMC + PEGD
VAL/VAC + NaCMC + PH
Soap
+ PH + PVP
VAL/VAC +
soap
+ china
clay
+ PH
VAL/VAC +
soap
+ NaCMC + PEGD
VAL/VAC +
soap
+ NaCMC + UN1
VAL/VAC +
soap
+ PH + UN1
VAL/VAC +
dye
+
polyamide
+ PH
VAL/VAC + NaCMC + PEGD + UN1
Soap
+ China
Clay
+ PH + PVAL
AYAA
(CR;SD), AYAC
(CR;SD), AYAF
(CR;SD),
AYAT
(CR;SD),
Vinac B-15
(CR;SD):
Aldrich PVAC
124800
(SD), Aldrich PVAC 194800 (SD), Aldrich PVAC 237100
(SD),
BDH PVAC
(CR;SD),
Lametec
(UF),
Mowilith 30 (CR;SD), Vinac ASB-516, Vinac B-25
(CR;SD), Vinac B-100
(CR;SD),
Vinavil K60
(CR;SD)
Sure-Grip Carpenter's (CR;E): Archival Aids
Tape
AFT1
(SF), Tufskin 4405
(E)
UHU Al
Purpose
Clear
(CR;SN)
Rabin's Mixture (CR;SN)
CM Bond M-2
(CR;E),
CM Bond M-3
(CR;E): Baystix
#502 Wood Glue
(E), Cascorez CV-815 (E), CM Bond
M-1 (CR;E), CM Bond W-5
(CR;E), Lepage's
Children's Glue
(E), Magna
Tac 1792
(E),
Nu Glu (E),
PVA 2500
(E),
PVA 2900
(E),
PVA 5000
(E),
R0065
(E), R9329(E), Rakoll-Express
25
(E),
Reichold ID-066
(E),
Swift's
2552 Resin (CR;E), Tanbond
Assembly (E),
Weldwood Presto Set
(CR;E),
Wood
Repair
Glue WRG-2
(E)
3M
Superbond
White Resin Glue
(E)
CM Bond W-4
(CR;E)
Gelva S-98 (E)
Promacto A-1023
(CR;E;B2;B3;B4)
Canada Standard PW2A
(E)
Euco Weld
(E),
Neutral
pH
White Adhesive (CR;E),
Swift's 2928
(E)
Elmer's Glue-All
(CR;E;B2), Weldbond (CR;E):
Adsol 604
(E),
BC #536
(E),
BC #4448
(E), Bulldog Grip
500
(CR;E),
C 847
(E),
C 852 (E), Mastercraft
All-Purpose (CR;E),
Planatol BB
Superior (E), R0530 (E),
Ultraflex
#4056 (E), Vinamul 9910 (E), White Glue
(CR;E)
Bondfast
(CR;E): Canada Standard PW625 (E),
Gelva S-52 (E), Gelva S-55R (E), Gelva S-77 (E), Gelva TS-85
(E)
Ponal (CR;E),
Resin 'W'
(E), Tufskin J5006 (E)
Titebond
(CR;E)
Gaylord Magic
Mend (CR;E)
Elmer's Glue-All
(CR;E;BO;B1),
Slomon's Velverette
(E)
Promacto A-1023 (CR;E;B1)
Bulldog Grip
2311
(CR;E)
Slomon's Sobo Glue
(E)
CM Bond W-3
(CR;E),
Gelva TS-30
(E)
Bulldog Grip
20 Min
(CR;E): Aquadhere
501
(CR;E)
Elmer's
Carpenter's
Glue
(CR;E)
CM Bond W-2
(CR;E)
Vinyl
Adhesive No. 6488
(E)
Additives
Vinyl
acetate /
ethylene copolymers
No additives Fusion 4000 (UF)*
VAL/VAC Vinamul 3254
(E)
Terpene phenolic
resin Kodak
Drymount
Tissue
Type
2
(SF)
VAL/VAC +
soap
Beva D-8 (CR;E), C-808 (E)
VAL/VAC + NaCMC Vinamul 3252 (E)
Soap
+ dextrin Jade No. 454
(CR;E)
VAL/VAC +
soap
+
polyacrylamide
Jade No. 403
(CR;E)
VAL/VAC +
soap
+ PEGD R-2258
(CR;E)
VAL/VAC +
soap
+ PH BC #4449 (E), Dopocol21 (E), Magna
Tac 1902 (E)
VAL/VAC +
soap
+ UN1 Elvace No. 1874
(CR;E), Vinnapas EP1 (CR;E)
KRN +
paraffin
+ PH Beva 371
(CR;SN)*
VAL/VAC +
soap
+ NaCMC + PEGD Slomon's Quik
Glue (E)
VAL/VAC +
soap
+ PH + UN1 CM Bond W-l
(CR;E)
Additives
Vinyl
acetate /
acrylic copolymers
VAL/VAC EC9722
(E)
PH Document
Repair Tape (SF)
Soap
+ NaCMC Vinamul 6815
(E)
VAL/VAC +
soap
+ UN1 Mowilith DM5 (CR;E): CM Bond M-4 (CR;E)
Additives
Vinyl
acetate / maleate
copolymer
Soap
+
methyl cellulose Mowilith
DMC2
(CR;E)
Selected adhesives are listed first in bold; BO, Bi, B2, B3,
B4 =
first, second, third, and fourth batches
analyzed;
CR = conservation referenced (sold by
a conservation
supply
house or in use in conservation); E
=
emulsion; KRN
=
ketone resin N; NaCMC
=
sodium
carboxy methyl cellulose; PEGD
=
poly(ethylene glycol) dibenzoate;
PH =
phthalate;
PVAL =
poly(vinyl alcohol); PVP
=
poly(vinyl pyrrolidone);
SD =
solid; SF
=
supported film; SN
=
solution; TS =
o,p-toluene
sulfonamide
plasticizer;
UN1
=
unidentified
peak
at 1125 cm4'; UN2
=
unidentified
peak
at 875 cm-'; UF
=
unsupported film; VAL/VAC
=
vinyl alcohol/vinyl acetate;
*
ethylene
predominates
in
copolymer
absorptions
of PVAC and
poly(vinyl alcohol)
which water were
centrifuged
at
3000rpm
to
separate
the
mask
absorptions
due to other
components.
products into
centrifugates containing
the water-
Therefore,
emulsions diluted with 10 volumes of insoluble resin
components
and
supernatants
con-
(1996)
19-44
Additives
20
Adhesive
testing
at the Canadian Conservation Institute
Table 2
Summary of
the results
of
the
analyses
of
the
acrylic
adhesives
for
adhesive selection
Acrylic type Homopolymers
MA
Acryloid C-O1LV
(SN)
EA
Rhoplex
LC-40
(CR;E):
Primal CA 12
(CR;E),
BA
Rhoplex
N-580
(CR;E): Rhoplex
PS-83-D
(CR;E)
EMA Elvacite 2028
(SD):
Elvacite 2043
(SD)
BMA
Acryloid F-10
(CR;SN): Acrysol
WS-24
(CR;E), Bedacryl
122X
(CR;SN),
Elvacite 2044
(CR;SD),
Formstar Clear
(CR;SN),
Lascaux P550-40 TB
(CR;SN),
Plexisol P550
(CR;SN)
iBMA
Acryloid
B-67
(CR;SD):
Elvacite 2045
(SD),
Elvacite 2046
(CR;SD)
Acrylic type Copolymers
MA/EMA
Acryloid
B-72
(CR;SD)
EA/MMA > 66% EA Pliantex
(CR;SN)
66% EA
Rhoplex
AC-33
(CR;E), Rhoplex
AC-234
(CR;E), Unsupported Texicryl
(CR;UF):
Plextol B-500
(CR;E), Rhoplex
AC-22
(E), Rhoplex
AC-634
(CR;E), Rhoplex
B-60A
(E), Rhoplex
MV-1
(E)
50% EA
Acryloid
B-82
(CR;SD), Rhoplex
AC-73
(CR;E)
< <50% EA
Acryloid
B-44S
(SN)
BA/iBA
Rhoplex
N-619
(CR;E)
BA/MMA 20-44%BA
Acryloid
B-48S
(CR;SN): Acryloid
B-50S
(SN)
56% BA
Rhoplex
AC-235
(CR;E):
Lascaux 498HV
(CR;E), Rhoplex
AC-61
(E),
Rhoplex
AC-64
(E), Rhoplex
AC-388
(E), Rhoplex
AC-707
(E)
> 50% BA Lascaux 360HV
(CR;E)
> >50% BA
Rhoplex
N-560
(CR;E)
MMA/BMA 40% BMA Elvacite 2013
(CR;SD)
50% BMA
Acryloid
B-66
(SD)
BA/acrylonitrile Rhoplex
N-1031
(CR;E): Rhoplex
LC-67
(E)
EA/MMA/EMA
Texicryl
13-002
(E)
MMA/BMA/EMA Plextol D360
(CR;E)
MMA/BMA/styrene Acryloid
B-99
(SN)
MA/iBMA/?
Acryloid
NAD-10
(SN)
Selected adhesives are listed first in
bold;
BA
=
butylacrylate;
BMA
=
butylmethacrylate;
CR conservation
referenced
(sold by
a conservation
supply
house or in use in
conservation);
E =
emulsion; EA
=
ethyl acrylate;
EMA
=
ethyl methacrylate;
iBA
=
iso-butyl acrylate;
iBMA =
iso-butylmethacrylate;
MA
=
methyl acrylate;
MMA =
methyl methacrylate;
SD =
solid;
SN =
solution;
UF =
unsupported
film
taining
the water-soluble
components.
The dried
residues from these fractions were
analyzed by
FTIR
using
a diamond cell
microsampling
acces-
sory.
Most
acrylic polymers
did not
separate
into frac-
tions when
centrifuged. Therefore,
no water-soluble
components
were detected
by
FTIR.
Only
the com-
position
of the resin
component
is
reported
for the
acrylic polymers.
The results of the PVAC and
acrylic analyses
are
summarized in Tables 1 and 2
respectively.
Selection of adhesives for
testing
was based on
these tables (one adhesive from each
chemically
similar
group)
and restricted to adhesives known to
the conservation
community.
Table 3 lists all the
adhesives selected. In
total,
27 PVAC and 25
acrylic
(1996)
19-44 21
J.L. Down, M.A.
MacDonald,
J. Tetreault and R.S. Williams
Table 3 List
of acrylic
and
poly(vinyl acetate) adhesives selected for testing
Acrylic Poly(vinyl acetate)
Acryloid
B-44S
(2) AYAA
(4)
Acryloid
B-48S
(3) AYAC
(3)
Acryloid
B-66
(2)
AYAF
(2)
Acryloid
B-67
(2)
AYAT
(2)
Acryloid
B-72
(2)
Beva 371 (2)
Acryloid
B-82
(2) Bondfast
(2)
Acryloid
B-99
(2) Bulldog Grip
20 Minute Resin
(3)
Acryloid
C-10-LV
(2) Bulldog Grip
R-2311
(3)
Acryloid
F-10
(2) CM Bond M-2
(2)
Acryloid
NAD-10
(2)
CM Bond M-3
(2)
Elvacite 2013
(4) Elmer's
Carpenter's
Glue
(2)
Elvacite 2028
(3)
Elmer's Glue-All (3)
Lascaux 360 HV
(3)
Elvace No. 1874
(2)
Pliantex (2) Gaylord Magic
Mend
(3)
Rhoplex
AC-33
(3)
Jade No. 403 (2)
Rhoplex
AC-73 (4) Jade No. 454
(2)
Rhoplex
AC-234
(4)
Mowilith DM5 (4)
Rhoplex
AC-234 +
Rhoplex
AC-73 Mowilith DM5 + Mowilith DMC2
Rhoplex
AC-235 (2)
Mowilith DMC2 (4)
Rhoplex
LC-40
(2) Promacto A-1023 (4)
Rhoplex
N-560
(2) R-2258 (3)
Rhoplex
N-580
(2) Rabin's Mixture
Rhoplex
N-619
(3) Sure-Grip Carpenter's
Glue (2)
Rhoplex
N-1031
(2) UHU
All-Purpose
Clear Adhesive (2)
Unsupported Texicryl (4)
Vinac B-15 (1)
Vinnapas Dispersion
EP1
(2)
Weldbond
(2)
Numbers in brackets indicate number of batches ordered
products
were
chosen,
which included a few mix-
tures of
products
used
by conservators,
some solid
PVAC resins with different molecular
weights,
and
products
with different forms
(i.e., solid, emulsion,
etc.).
There is
always
concern that formulators could
change products
and thus invalidate the results of
tests conducted. To evaluate the extent of this
problem, samples
from
separate
batches ordered
over a
period
of six
years
were
analyzed
for 24
acrylics
and 24 PVACs. The number of batches
analyzed ranged
from two to four
(two
batches for
29
adhesives,
three batches for 11
adhesives,
and
four batches for
eight adhesives).
Of these 48 adhe-
sives, only
two
PVACs,
Elmer's Glue-All
(one
of
three
different)
and Promacto A-1023
(one
of four
different),
showed minor batch-to-batch differences
(see
Table
1).
No differences between batches were
detected
by
this
analytical procedure
for the other
46 adhesives.
Notwithstanding
this
good
track
record,
it is
always possible
for formulators to
change
their
products
without notice and the reader
is warned of this
possibility.
Aging
conditions
Dark
aging
at 22?C and 45% relative
humidity
(RH)
was carried out in
enclosed,
melamine-lami-
nated, particle-board cupboards.
The
samples
were
laid on screen
shelving,
with box fans
venting
the
air to
prevent
unwanted volatile chemicals from
accumulating. Light aging
was carried out under
40watt Duro Test Vita-Lite fluorescent
lights
at
700-8001ux, 190jWlm-1 (proportion
of UV radia-
tion in the 300-400nm
range),
22?C and 45% RH.
The
light-aging
racks were constructed of Dexion
adjustable
metal
framing
from which the fluorescent
lights
and melamine
shelving
were
suspended.
The
fluorescent
lights
were
suspended
about 50cm above
the
sample shelves,
and
screening
was used to
reduce the
intensity
and
non-uniformity
of the
light
distribution. Box fans ran
continuously
to remove
heat from the fluorescent
lamps.
The
samples
were
exposed continuously
to the
lamps.
In real museum
conditions, lights
are not on
continuously
and
may
be at lower
intensity.
Based
on a
typical
museum
exposure
of 3000 hours
per
year (six days
a
week,
10 hours a
day),
five
years
of
continuous
exposure
under these
experimental
con-
ditions is
equivalent
to about:
15
years
in a museum at
700-8001ux, 190uWlm-1
or
50
years
in a museum at
2001ux, 190Wlm-'
or
200
years
in a museum at
501ux, l90uWlm-
.
Acidity
or
alkalinity
If an adhesive in contact with an artifact is too
acidic or too alkaline it
may
accelerate deteriora-
tion. The most suitable adhesives for conservation
(for
most
applications)
are those with neutral
pH
and those that remain so
upon aging.
Since
pH
gives
a measure of
acidity
and
alkalinity,
this
prop-
erty
was included in the
testing.
pH procedures
Two methods for
measuring pH
were
adopted,
one
for
measuring
the
pH
of extracts of the
dry
adhe-
sive film and one for
measuring
the
pH
of the wet
emulsion. The first method
gave
an indication of
the
long-term acidity/alkalinity
of a dried adhesive
in direct contact with an
object.
The second method
focused on the effect of shelf-life on emulsion
pH.
pH of
extracts
of dry
adhesive
films
After
assessing
several
procedures,
a modified
[2]
ASTM test method
[4]
was
adopted.
The
procedure
was chosen for its
lengthy
extraction
period
which
was found
necessary
to extract all the acidic and
basic
components, especially
from the
hydrophobic
acrylic
adhesives. The extent of acid
migration
from
an adhesive into an artifact could
depend
on a host
of circumstances
including
the nature of the adhe-
sive and the substrate
(artifact),
and ambient condi-
tions. The method chosen took into account
(1996)
19-44 22
Adhesive
testing
10
9
8
7
I-
CL
6
?
i t
i
' i 2 Xas o
CN 0 o.
r
0-10 1
3
0
I
I
I
Unacceptable I
NO ADDITIVES
WITH ADDITIVES WITH ADDITIVES
HOMOPOLYMERS COPOLYMERS
Figure
1
pH of
extracts
of
dried P VA C adhesive films after two,
three and
four years of
dark
aging,
and
one, two and three
years
of light aging (see
Table 4
for data).
Also
pH of
P VAC emulsions
(where applica-
ble) after
three and
five years of dark storage. Each cluster
of points represents
an adhesive. Adhesive clusters
are
grouped according
to chemical
composition
(see
Table 1).
situations where the adhesive
might
be held in moist
conditions for
prolonged periods.
A method
using
a
short extraction time would
only identify
adhesives
with acid
components that
migrate quickly.
The chosen method involved
pouring
films of
each adhesive onto Teflon release
paper
and allow-
ing
them to
dry
for one month. The initial
pH
mea-
surement was taken at this time. The films that
remained were divided in two and
placed
in the two
aging environments; pH measurements were taken
on water extracts of these films
annually
thereafter.
pH
was monitored for about four
years
of dark
aging
and for about three
years
of
light aging.
The
procedure
for
measuring pH
involved
cutting
or
grinding enough dry
adhesive for
triplicate
sam-
ples
and
weighing 2g
into each vial. Glass-distilled
Nanopure
filtered water
(10ml, pH
between 6-5 and
7-3)
was
pipetted
into each vial. The
samples
were
shaken and allowed to extract for 72 hours before
the
pH
of each
sample
was measured.
pH
measure-
ments were then taken at 24 hour intervals until the
difference between consecutive
readings
was not
greater
than 0.05
pH
units. The last
reading
was
recorded as the
equilibrium
film
pH
value of that
sample.
pH of
wet emulsions
The
pH
of the wet emulsion was measured
shortly
after
receiving
the
product.
A
quantity (about
100ml)
of each emulsion
product
was sealed in an
opaque
vial and stored in the dark at room
temper-
ature. The
pH
of the emulsion was re-measured
after three and five
years.
pH
results
Tables 4 and 5
along
with
Figures
1 and 2
present
the
updated
results of the
pH
measurements on the
PVAC and
acrylic
adhesives.
An
acceptable
adhesive was defined as one whose
(1996)
19-44 23
4v Table 4 Results
of
the
pH
measurements on the emulsions and on
dry film
extracts
of
the
poly (vinyl acetate)
adhesives
Adhesive pH
Emulsions
Dry film
extracts
Control Dark
aging
Control Dark
aging Light aging
-0
year
-3
years
-5
years
-0
year
-2
years
-3
years
-4
years
-1
year
-2
years
-3
years
5.71 5.96
4.22 6.09
5.06 6.14
a5.48 6.23
7.57 7.15
6.89 A6.45 4.58
6.86 6.56 4.49
6.76 6.26 4.98
6.56 6.09 4.99
7.64 a7.61 a6.20
Bondfast
Bulldog Grip
20 Minute Resin
Bulldog Grip
R-2311
CM Bond M-2
CM Bond M-3
Elmer's
Carpenter's
Glue
Elmer's Glue-All
Elvace No.1874
Gaylord Magic
Mend
Jade No.403
3.75
4.65
4.64
4.31
4.51
4.31
4.49
4.01
4.47
5.80
Jade No.454 3.84
ca Mowilith DM5 4.48
H
Mowilith DM5 + Mowilith DMC2 4.02
Mowilith DMC2 4.01
Promacto A-1023 4.23
o
R-2258
m Rabin's Mixture
Sure-Grip
UHU All
Purpose
Clear Adhesive
x Vinac B-15
.1&
6.58
3.81
3.65 3.56 4.01 4.04
4.47 4.82 4.55 4.24
6.84
mouldy
4.87 4.84
4.73 4.90 4.38 4.40
6.99 too thick 4.04 3.84
4.47 4.49
4.60 4.62
4.12 4.04
4.53 4.32
5.43 5.62
4.35 4.28
4.69 4.73
4.39 4.38
4.13 4.70
7.04 7.09
3.49 3.32 4.14 4.32
3.78 3.73 a3.91 4.43
4.03 too thick 5.71 6.92
3.80 too thick 6.62 6.67
6.12 too thick 4.51 5.18
6.44 too thick 6.55 a6.30
- -
a6.52 6.27
3.72 3.61 4.28 4.14
- - 4.89 4.89
-4.05 6.26
4.10
4.52
4.90
4.51
3.88
- 4.01
4.43
4.83
4.37
3.74
4.36 - 4.21
4.97 -
4.75
4.57 -
4.20
4.87
-
4.58
7.29 7.05 5.96
4.58
-
4.22
a7.06 b6.81 4.10
6.89 6.89 6.34
6.68 6.59 6.46
5.81 -
4.10
6.47
6.81
4.30
4.86
6.21 5.38
6.41 3.86
-
4.03
-
4.04
-
4.03
Vinnapas Dispersion
EP1 3.81 3.37 3.23 5.08 6.32 7.28 a7.29 4.74 4.89 6.29 >
Weldbond 4.74 4.77 4.64 5.46 5.02 5.24
-
4.81 4.84
-
o Values for emulsions indicate a
single measurement;
Values for
dry
film extracts indicate the mean of
triplicate samples;
Standard deviations for
dry
film extracts are o
1 %
except
where
indicated;
a
Indicates standard deviation of 2-3
%;
b Indicates standard deviation >3 %
-PI~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
AYAA
AYAC
AYAF
AYAT
Beva 371
b5.80
a4.76
a6.64
5.24
6.39
4.45
4.38
4.67
4.63
4.07
4.26
4.89
4.41
3.75
4.28
4.80
4.21
4.70
6.26
4.30
4.01
6.52
6.43
3.85
4.72
3.97
4.34
3.74
o
I
6.36 .
-
I
5.61
6.25
?
-
~F~ -
4.36
l
3.77
-
- I-
- z
IZ
7Cl Table 5 Results
of
the
pH
measurements on the emulsions and on
dry film
extracts
of
the acrylic adhesives
M'
Adhesive
A
Acryloid B4 Acryloid
B-44S
Acryloid
B-668S
Acryloid B-66
Acryloid B-67
_
1Acryloid
B-72
Acryloid B-82
Acryloid
C-10-LV
Acryloid C-10-
Acryloid
P-10
Acryloid
NAD-10
Elvacite 2013
Elvacite 2028
Lascaux 360 HV
Pliantex
Rhoplex
AC-33
pH
Emulsions
Dry film
extracts
Control Dark
aging
Control Dark
aging Light aging
-O0
year
-3
years
-5
years
-O0
year
-2
years
-3
years
-4
years
-2
years
-3
6.72
3.84
a5.96
6.68
6.41
6.41
b5.77
b5.45
6.73
4.61
7.79
9.35
7.35 7.30
8.27 8.25
6.63
6.51
7.01
5.93
5.88
6.64
4.22
a6.37
6.42
6.42
6.61
6.28
a6.16
6.57
4.75
6.60
6.56
6.82
5.56
5.17
6.70
4.07
6.47
6.77
6.63
6.54
6.31
6.17
6.71
5.01
7.01
6.51
6.89
5.87
5.15
a6.59
4.22
4.87
6.33
6.23
a5.63
b6.10
5.15
6.60
4.37
6.75
5.93
6.68
5.04
5.54
6.72
3.69
4.49
7.41
b5.93
6.65
a6.40
6.42
6.01
4.44
6.56
6.42
6.54
4.36
4.40
years
<t
6.34
4.05
?
4.41
Q
6.66
Z'
4.70
a
a5.67
6.17 t
s
'
6.20
1s
4.17
|
a6.07
b5.53
5.68
3.88
3.71
Rhoplex
AC-73
Rhoplex
AC-234
Rhoplex
AC-234 +
Rhoplex
AC-73
Rhoplex
AC-235
Rhoplex
LC-40
Rhoplex
N-560
Rhoplex
N-580
Rhoplex
N-619
Rhoplex
N-1031
Unsupported Texicryl
9.59
9.15
9.32
9.63
4.02
7.40
8.03
6.64
7.94
9.18
8.82
8.95
9.11
3.88
6.68
7.65
5.76
7.75
9.01
8.71
8.86
8.86
4.05
6.74
7.52
5.65
7.69
a6.50
6.46
6.75
6.39
4.38
7.09
7.04
6.98
7.23
4.49
5.81
5.37
5.24
4.19
7.06
6.56
6.64
86.43
c4.06
4.34
5.46
5.38
4.82
4.14
a7.06
6.70
6.96
6.42
ad4.73
4.14
5.81
5.10
84.89
4.12
6.70
6.06
6.25
6.10
e6 .40
3.62
5.22
5.13
3.88
4.50
6.90
6.38
6.59
a6.46
3.67
3.40
4.24
84.45
3.49
4.08
6.60
6.15
b6.02
5.89
Values for emulsions indicate a
single measurement;
Values for
dry
film extracts indicate the mean of
triplicate samples;
Standard deviations for
dry
film
extracts are <2%
except
where indicated;
a
Indicates standard deviation of
3-4%;
b Indicates standard deviation
>4%;
c
Aged
3
years;
d
Aged
3.5
years;
e
Aged
4.5
years
J.L.
Down,
M.A. MacDonald,
1 0 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
* Dark
Aged
Films
0
Light Aged
Films
v Dark
Aged
9
_ Emulsions
7
?
% 7v o
7
Unacceptable
4-
o ^o 1V
I0
CO
Oi
o, +
x o z o
0 -1 0
00
m
^
+ 0
m p
8 'B
?0
v,
o,
?
. ._ 2
?
S
|P
SC
z 0
v
,
a I
Iu
I I
m
I i I I I
":
g ?
s
*.
6o-p
I ucodn
<
c o
-
Acceptable
11
I-
- '
I ^
L
i
.^
^T^
'*I T
nI .2
7- '5 ?
rf
a
I
r
I
.-
<
.tio
r
u c
070
0
ID
O
6o
0 o o >'
4 Oh
I
I
I
L) r
0
5-
?0
0 -10
xCRY ACHTESPEA/PMMA PBA/PMMA
-'grouped
a r
Unacceptable
AGING TIME (years)
(D
0 -10
MIETH_
Figure
2
pH of
extracts
of
dried acrylic adhesive
films after two, three and
four years of
dark aging,
and two
and three
years of light aging (see Table
5
for data). Also pH of acrylic
emulsions (where applicable) after
grouped according
to chemical
composition (see Table 2).
extract
pH
was in a
range
that could be tolerated
without
damage by
most artifacts. Since artifacts
are
composed
of
many
different materials which
possess varying
tolerances to acid and
alkali,
it is
difficult to set universal
pH ranges. However,
a
pH
range
that can be tolerated without
significant
dam-
age by
most materials was chosen based on the fol-
lowing
information.
Textiles with extract
pH
in the
range
5.5 to 8.5
have been
accepted
for use with
organic
artifacts in
permanent
exhibitions
[5, 6].
Research on
paper
and cellulosic material
[7-10]
has shown that cellu-
losics
degrade
and become brittle when extract
pH
is below
5.5,
are
only slightly
unstable when
pH
is
between 5.5 and
6.0,
and are stable when
pH
is
neutral or alkaline
up
to
pH
10. This alkali toler-
ance is reflected in the ANSI standard
[11]
which
specifies
that
permanent paper
should have a mini-
mum
pH
of 7-5 and alkaline reserve of 2% calcium
carbonate. Steel corrodes
slowly
in water between
pH
43 and 10 but
rapidly
below this
pH range
[12].
Woods with cold
aqueous
extracts above
pH
5-0-5-5 are
moderately
corrosive to
metals,
while
those with
pH
less than 5.5 are
highly
corrosive
[13].
For
storage
of black-and-white
gelatin
emul-
sion
photographs, paper
with a
pH
between 7.2 and
9.5 and an alkali reserve
equivalent
to 2% calcium
carbonate is
recommended;
for colour
photographs,
however,
non-buffered
paper products
with a
pH
of
7-0-7-5 are
specified,
due to the alkaline
sensitivity
of colour
image dyes [14].
There are some
argu-
ments that this
latter,
neutral
pH range
is more
appropriate
for albumen
prints
than the former
more alkaline recommendations
[15].
At their iso-
electric
point, proteins
are most
tightly coiled,
least
soluble in water and most stable. The isoelectric
points
of
collagen
and its
aqueous
extracts
vary
from about
pH 5,
for
lime-processed gelatin
from
which
photograph
emulsions are made
[9],
to about
pH
9 for native
collagen [16].
(1996)
19-44 26
Adhesive
testing
Based on these
observations,
the
acceptable pH
range
was set at 5 5-8-0 and can be seen to the
right
in the
figures.
In the authors'
opinion,
most
artifacts will not be affected
significantly by
contact
with adhesives
having
an extract
pH
in this
range.
Since some artifacts are more stable in acid or alka-
line
conditions,
these so-called
acceptable
adhesives
are not
always
the most suitable for
particular
applications. Furthermore,
it must be remembered
that extract
pH
measures
only
the
acidity
of mater-
ial extracted from the solid mass of the adhesive.
Any
volatile acids and alkalis that are
produced by
the adhesive as it
degrades evaporate
from the
adhesive and are therefore not dissolved in the
water
during
extraction and do not contribute to
the measured
pH.
The
possibility
that these volatile
acids and alkalis
might
cause
damage
to artifacts
must be considered when
assessing
adhesive suit-
ability
and is examined in the 'Volatile emissions'
section of this
paper.
pH
discussion
The
following general
trends are evident from the
results:
(1)
Extracts of
dry
PVAC adhesive films are
gener-
ally
more acidic than those of
acrylic
adhesive
films.
Figures
1 and 2 show that more
acrylic
than PVAC adhesives fall into the
acceptable
pH range.
(2)
In most
cases, light aging
tends to decrease the
extract
pH
of the adhesive.
Within the PVAC
class,
the
following general
observations were made:
(1)
The
majority
of the PVAC
dry
adhesives were
acidic.
(2) Homopolymers
with additives showed a ten-
dency
to be more acidic than
copolymers.
(3)
Additives tended to lower the
pH
of the PVAC
adhesives.
(4)
The PVAC emulsions
(i.e.,
in the wet
form)
were acidic
(pH<5).
Most became more acidic
upon storage
for three to five
years.
(5)
The solid PVAC resins
(AYAA, AYAC,
AYAF,
AYAT and Vinac
B-15)
were
initially
acidic but became less so
upon
dark
aging.
They
remained acidic after
light aging.
(6) Only
the
pH
of the PVAC adhesives Beva
371,
Jade No.
403,
Mowilith DMC2 and Mowilith
DMC2 + DM5 fell within the
acceptable range
initially
and after
aging.
Within the
acrylic class,
the
following general
observations were made:
(1)
The
pH
of most of the
acrylic
adhesives fell
within the
acceptable range.
(2) Considering only
the
copolymers,
a few trends
emerged:
(a)
For the
ethyl acrylate/methyl methacrylate
copolymers,
the
products
with less
ethyl
acrylate
were closer to
neutrality
than those
with more.
(b)
For the
butyl acrylate/methyl methacrylate
copolymers,
the
products
with more
butyl
acrylate
were closer to
neutrality
than those
with less.
(3)
The
acrylic
emulsions
(i.e.,
in the wet
form)
were alkaline
(pH>8).
Most emulsions
initially
measured between 9 and 10. After three to five
years
of
storage,
the
pH
fell to between 8 and 9.
(4)
The
Rhoplex
emulsions
AC-33, AC-73,
AC-234
and AC-235 were alkaline
(about pH 9),
while
their
dry film
extracts were neutral. After these
Rhoplex
films were
light aged,
their
pH
fell into
the acidic
range (pH<5).
For treatments and
applications
where
pH
is of utmost
concern,
changes
of this order are
unacceptable.
(5) Unsupported Texicryl initially gave
a low
pH
(4-2) but,
after
aging
in the
dark,
the
pH
was
closer to
neutrality. Texicryl
remained acidic
under
light aging.
(6) Acryloid
B-72 remained neutral under dark
aging
but measurements of
samples
after three
years
of
light aging gave
a
pH
of 4-7. Because
Acryloid
B-72 is so
important
to the conserva-
tion
community,
a measurement at 5.5
years
of
light aging
was
recently
taken and found to be
within the neutral
range (pH 6.25). Currently,
we have no clear
explanation
for this
phenome-
non.
(7) Acryloid B-44S, Acryloid B-67, Acryloid B-82,
Acryloid B-99, Acryloid F-10,
Elvacite
2013,
Elvacite
2028,
Lascaux 360
HV, Rhoplex
N-
560, Rhoplex N-580, Rhoplex
N-619 and
Rhoplex
N-1031 were the
acrylic
adhesives clos-
est to
neutrality,
and were the ones that
remained so over time.
Volatile emissions
In closed
systems,
such as well-sealed
display cases,
closed
storage
containers or
encapsulated
enclo-
sures,
the
presence
of acids in the emission
products
(1996)
19-44 27
Table 6
Summary of
the emission
of
volatiles from the
poly(vinyl acetate)
adhesives
Adhesives Dark
aging Light aging
pig
acetic acid emitted/ g adhesive Other volatiles emitted
,g
acetic acid emitted / g adhesive Other volatiles emitted
-3 mos -1
year
-2
year
-3
year
-3 mos -I
year
-2
year
-3
year
AYAA a0.4 <0.5 <0.2
-
4, 10, 14 <0.2 <0.5 <0.2
-
2, 4, 5, 10,
14
AYAC <0.2 <0.5 <0.2
-
10, 14 <0.2 <0.5 <0.2
-
10,
14
AYAF a0.3 <0.5 <0.2
-
10,
14 <0.2 <0.5 <0.2
-
10, 12,
14
AYAT <0.2 <0.5 <0.2
-
4, 5, 10,
14 <0.2 <0.5 <0.2
-
2, 10, 14,
17
Beva 371 <0.2 <0.5 <0.5
-
13, 14, 22 <0.2 <0.5 <0.5
-
13, 14,
22
Bondfast 3.8 6.0 7.8 0.33
4, 5, 8, 9, 11, 14,
18 33.1 4.1 13.0 a0.25
14, 18,
20
Bulldog Grip
20 Min 0.5 a2.0 2.7 <0.02
4,
14 5.9 1.4 6.3 <0.02 2, 4, 14,
22
Bulldog Grip
R-2311 <0.5 a0.2 0.7 <0.02 14 a5.4 <0.2 2.2 <0.02 14
CM Bond M-2 11.1 1.9 <0.2
-
5, 10, 14, 17 a17.7 1.5 <0.2
-
5, 8, 10, 14,
17
CM Bond M-3 <0.5 1.9 0.6 <0.02 4, 5, 10, 14 a1.9 0.2 1a.2 <0.02 2, 10,
14
Elmer's
Carpenter's
'0.7 '2.1 a0.8 <0.02 4, 14 5.4
a0.8
1.4 <0.02 14
Elmer's Glue-All 1.1 1.4 a0.6 <0.02
1, 2, 5, 14, 17,
22 a5.5 0.8 1.2 <0.02 14, 17, 22
Elvace No. 1874 <0.5 0.6 '0.7 <0.02
4,
14 a2.7 a0.9 1.5 <0.02 14
Gaylord Magic
Mend <0.5 <0.2 <0.5 <0.02 14 al.0 <0.2 <0.5 <0.02 14
Jade No. 403 0.6 '0.3 <0.5 <0.02
4, 5, 8, 14,
15 0.8 <0.2 <0.5 <0.02
2, 4, 5,
14
Jade No. 454 2.0 3.1 a2.2 '0.15 12, 14, 16, 19,
20 25.1 al.2 a3.0 <0.02 12, 14, 16, 19, 20
Mowilith DM5 0.6 1.9 a0.7 <0.02 8, 14, 19,
20 6.8 0.9 1.8 <0.02 8, 14,
20
Mowilith DM5 + DMC2 14.9 a2.6 <0.5
-
3, 8, 14, 15, 17,
22 '22.3 a1.3 <0.2
-
3, 8, 14, 15, 17,
22
MowilithDMC2 <0.5 3.1 a2.4 <0.02 2, 4, 7, 8, 14, 15, 20,
22 9.4 1.0 2.1 <0.02 7, 8, 14, 15,
17
Promacto A-1023 <0.5 0.5 ^0.7 <0.02 2, 4, 8, 10, 14, 15, 20, 22 <0.5 <0.2 1a.1 <0.02 4, 14, 16,
17
R-2258 <0.5 "0.2 <0.5 <0.02
9, 12, 14, 20,
22 a3.7 <0.2 <0.5 <0.02 2, 12,
14
Rabin's Mixture <0.2 <0.5 <0.2
-
4, 5, 10, 12, 13,14
<0.2 <0.5 <0.2
-
5, 10, 11, 12, 14, 17
Sure-Grip Carpenter's
2.6 3.9 a1.2 0.03
14,
22 45.1 1a.5 a3.4 a0.09
14,
22
UHU
All-Purpose
Clear <0.5 a0.3
a0.6
<0.02 5, 14, 21,
22 <0.5
a0.2 a0.8
<0.02 5, 6, 14, 17,
21
Vinac B-15 <0.2 <0.5 <0.2
-
4, 10, 12,
14 <0.2 <0.5 <0.2
-
2, 10, 12, 14,
17
Vinnapas Dispersion
EP1 0.8 1.6
a1.4
<0.02
5, 14,
21 19.0
a0.8
a2.1 <0.02 14
Weldbond <0.5 1.2 0.9 <0.02
5,
14 8.7 a0.4 a0.9 <0.02
2,
14
Values indicate mean of 2
samples;
Standard deviations are <25%
except
where
indicated;
a
Indicates standard deviation >25%; <0.02,
<0.2 and <0.5 indicate the limit of
detection;
1 = formic acid;
2 =
acetaldehyde;
3
=
butyl acetate;
4 =
ethyl acetate;
5 =
methyl acetate;
6 =
methyl formate;
7 =
isobutanol;
8 =
n-butanol;
9 =
t-butanol;
10
=
ethanol;
11
=
benzene; 12 =
toluene;
13 =
xylene;
14
=
water;
15
=
dibutyl ether;
16 =
dichloromethane;
17 = ethanediol diacetate;
18
= ethanediol monoacetate;
19
=
2-ethoxy ethanol;
20
=
2-ethoxy ethyl acetate;
21
=
2-methoxy ethyl acetate;
22
=
unknown
o0 00
Adhesive
testing
of the adhesives
poses dangers.
To determine the
amount of volatile
compounds
emitted from dried
adhesive
films,
a new test was
designed,
one that
would
help
to evaluate the
suitability
of adhesives
used in the
vicinity
of artifacts
(for instance,
in dis-
play
or
storage situations)
as
opposed
to adhesives
used
directly
in contact with an artifact.
Volatile emission
procedure
Since the
original experiments
for volatile emis-
sions,
which were conducted from 1986 to 1988
[2],
did not involve
light aging
of
samples
and
only
one
measurement after dark
aging
was
taken,
the
proce-
dure was
repeated
to include
light aging
and more
measurements. The
experimental procedure
fol-
lowed was similar to the
original experiment except
that vials with
screw-top septa replaced ampoules
so that
repeated sampling
could be
performed.
It
was
found,
much
later,
that these vials leaked
slowly
but
consistently. Thus, although
the mea-
sured
quantities
were not
absolute, they
did indicate
the adhesives that released
high
amounts of volatile
compounds.
In
reality,
these vials model the actual
situation of adhesives in enclosed environments.
The volatile emissions
procedure
involved
pour-
ing
adhesive
products
onto Teflon release
paper
and
allowing
them to
dry
for one month in the
dark to eliminate
any
volatiles due to the film cur-
ing.
The
dry
films
(5g)
were shredded or
ground,
enclosed in
glass
vials with
septum
and allowed to
age.
Four
samples
for each adhesive were
prepared,
two for dark
aging
and two for
light aging.
After
timed
aging
intervals, the
airspace
in the vials was
sampled using
a
gas-tight syringe.
Each
sample
was
injected
into a Hewlett-Packard Model 5890A
gas
chromatograph
with a mass-selective detector
(GC-
MSD) (DB
wax fused silica
capillary column;
helium carrier
gas; temperature programmed
from
35 to
200?C).
The amounts of acetic acid were
determined
quantitatively;
other
compounds
were
identified but
only qualitatively.
The PVAC adhesives were
sampled
at three
months,
one and two
years,
while the
acrylic
adhe-
sives were
sampled
at one and two
years only.
After
sampling,
the vials were aired for 24 hours
before
being
resealed.
PVAC volatile emission results
Two
possible
sources of emanation of acetic acid
vapour
from the PVAC adhesives are free acetic
acid in the formulation or
hydrolysis
of the acetate
side-group
on the
polymer upon aging.
The PVAC emission results are summarized in
Table 6.
During
the first
year
of
aging,
over half
the PVAC adhesives released measurable
quantities
of acetic acid. The
highest
amount measured was
45-
1ig
acetic acid
per gram
of dried adhesive.
Adhesives released the
highest
amounts of acetic
acid within the first
year,
with the amounts decreas-
ing significantly
for each successive
year
of
aging.
In
general,
the adhesives emitted the most acetic
acid when
light aged
for the first three months.
PVAC
homopolymers
and
copolymers
released
similar amounts of acetic acid. Solid PVAC adhe-
sives tended to release less acetic acid than did
emulsion
products.
Elmer's Glue-All released
formic acid
(methanoic acid),
the
only
other acid
emitted from the PVAC adhesives.
The
presence
of
aldehydes
could
pose
a
problem
for artifacts.
AYAA, AYAT, Bulldog Grip
20
Minute
Resin,
CM Bond
M-3,
Elmer's
Glue-All,
Jade No.
403,
Mowilith
DMC2,
Promacto
A-1023,
R-2258,
Vinac B-15 and Weldbond all released
acetaldehyde (ethanal).
The PVAC adhesives emitted various esters-
butyl acetate, ethyl acetate, methyl
acetate and
methyl
formate. The threat
posed by
these com-
pounds
has not been
clearly
established. These
esters,
like PVAC
itself,
should not
pose
a
problem
unless
hydrolyzed
to acids. Since water alone does
not
hydrolyze
most esters
[17], hydrolysis
could
occur
only
if an acid is
already present,
as with the
adhesives that release
high quantities
of acetic acid
(e.g.,
CM Bond M-2 or Mowilith DM5 +
DMC2).
The PVAC adhesives also released
alcohols,
aro-
matic
hydrocarbons, water,
ethers and chlorinated
hydrocarbons.
These are considered
relatively
harmless to artifacts in the amounts found.
Several
compounds,
such as ethanediol
diacetate,
ethanediol
monoacetate, 2-ethoxyethanol, 2-ethoxy-
ethyl
acetate and
2-methoxyethyl acetate,
were
identified in the emission
products
of some of the
PVAC
products.
These are
thought
to be
degrada-
tion
products
from the GC-MSD column
[18].
Acrylic
volatile emission results
The
acrylic
emission results are summarized in
Table 7. The
only acrylic
adhesive that released
any
acid was Lascaux 360
HV,
which emitted low
quan-
tities of acetic acid. Elvacite 2028 emitted acetalde-
hyde.
The esters released
by
the
acrylic
adhesives
included
butyl crotonate, ethyl acetate, isobutyl
acrylate, methyl
acetate and
methyl methacrylate.
The
acrylic
adhesives also released
alcohols,
aro-
matic
hydrocarbons,
water and ethers. As with the
PVACs,
these should be
relatively
harmless.
Volatile emission discussion
For
many artifacts,
the level at which acetic acid
vapour
causes
damage
is not known.
Therefore,
it
(1996)
19-44 29
J.L.
Down,
M.A. MacDonald, J. Tetreault and R.S. Williams
Table 7 Summary of
the emission
of
volatiles
from
the
acrylic
adhesives
Adhesives Volatiles emitted
Dark
aging Light aging
Acryloid
B-44S 7, 9, 14, 15, 16, 18 5, 7, 9, 14, 15, 16, 18
Acryloid
B-48S
3, 5, 7, 14, 15 3, 5, 7, 14, 15, 16
Acryloid
B-66 14, 16, 18 14, 16
Acryloid
B-67 7, 12, 13, 14, 16, 18 14, 15, 16, 18
Acryloid
B-72 14 14, 16
Acryloid
B-82 14
14, 16
Acryloid
B-99 3, 5, 10, 11, 14, 15, 16 3, 7, 11, 14, 15, 16, 18
Acryloid
C-10-LV 3, 11, 14, 15, 16 11 , 14, 15, 16, 18
Acryloid
F-10 7, 14, 16, 18 6, 14, 16, 18
Acryloid
NAD-10 14, 15, 16, 18 14, 15, 16, 18
Elvacite 2013 14 14, 16
Elvacite 2028 2, 14, 15, 16 14, 15, 16, 18
Lascaux 360 HV 8, 16 1, 8, 11, 14, 15, 16
Pliantex 14, 16 10, 14, 15, 16, 18
Rhoplex
AC-33 10, 16 6, 9, 10, 14, 16
Rhoplex
AC-73 14, 16, 18 6, 10, 14, 16
Rhoplex
AC-234 14, 16 10, 14, 15, 16
Rhoplex
AC-234 + AC-73 14, 16 6, 10, 16
Rhoplex
AC-235 8, 16, 17 6, 15, 16, 17
Rhoplex
LC-40 10, 16 10, 15, 16, 18
Rhoplex
N-560 8, 14, 16 8, 14, 16
Rhoplex
N-580 14, 15, 16, 18 6, 8, 14, 15, 16
Rhoplex
N-619
5, 8, 14, 15, 16, 18 5, 6, 8, 14, 15, 16
Rhoplex
N-1031 14, 15, 16 3, 8, 14, 15, 16
Unsupported Texicryl 10, 14, 15, 16 3, 14, 15, 16
1 = acetic acid; 2 =
acetaldehyde;
3
=
butyl crotonate; 4 =
ethyl acetate; 5 =
isobutyl acrylate; 6 =
methyl acetate; 7
=
methyl methacrylate;
8
=
n-butanol; 9 =
t-butanol;
10 =
ethanol; 11 =
methanol; 12 =
1,2,3,4-tetra methyl benzene; 13 =
2-ethyl, 1,3-dimethylbenzene;
14 =
toluene; 15 =
xylene;
16 =
water; 17 =
dibutyl
ether; 18 = unknown
is not
possible
to determine with
certainty
the haz-
ard
posed by any
of the PVAC adhesives. The haz-
ard
posed by organic
acids to various metals is
documented
[19, 20].
Acetic acid will cause corro-
sion of lead at levels around
0.5ppm
at 22?C and
54% RH
[20].
To obtain such a concentration in a
0.0283m3
(one
cubic
foot) hermetically
sealed dis-
play case, lg
of dried adhesive would have to
release
35pig
of acetic acid. Several of the PVAC
adhesives
approached
this level in the first three
months of
light aging: Sure-Grip (45-lugg-'),
Bondfast
(33.lpgg-),
Jade No. 454
(25-llgg1),
Mowilith DMC2 + DM5
(22-3,gg-'), Vinnapas
Dispersion
EP1
(19-0,ygg-);
and in the first three
months of dark
aging:
Mowilith DMC2 + DM5
(14-9ygg-),
CM Bond M-2
(ll-lgg-1).
Since even
the best-sealed
display
case
leaks,
doubt exists as to
whether the
quantities
emitted
by
even these PVAC
adhesives should
pose
a
problem
to lead.
In a
separate experiment,
it was shown that
increasing
levels of volatile acetic acid in a closed
environment resulted in a
corresponding
decrease in
paper pH.
Even
though
the level at which this
would result in actual
damage
to the
paper
was not
determined,
it is more
likely
to take
place
at the
higher
levels. There are
many
situations where
paper
or other acid-sensitive artifacts are held in
close
proximity
to an adhesive for
prolonged peri-
ods
(for example,
in a book or in a closed
box).
In
such
cases,
the levels of volatile acetic acid detected
in some of the PVAC adhesives
may
be sufficiently
high
to affect the
paper
or artifact
adversely.
Although
this risk assessment
requires
more
study,
it does seem
that,
after the initial
curing
period
of one month
[21],
the evolution of acetic
acid from most PVAC adhesives will not
pose
an
acute hazard to most substrates under normal cir-
cumstances.
However,
it would seem
prudent
to
avoid the adhesives that
give
the
higher
emissions
of acetic
acid, especially
when there
may
be
pro-
longed exposure
in an enclosed
space.
Air
drying
the adhesive for one month
prior
to enclosure is
strongly
recommended.
Volatile acetic acid data were examined in rela-
tion to the
pH
data for the PVAC adhesives.
Despite
the
large variability,
the
general
trend is
that the lower the
pH,
the
higher
the emission of
acetic acid.
The
following
adhesives released the lowest levels
of acids and would be the most suitable in terms of
volatile emission: all
acrylic adhesives, AYAA,
AYAC, AYAF, AYAT,
Beva
371,
Jade No.
403,
Rabin's
Mixture,
UHU
All-Purpose
Clear Adhesive
and Vinac B-15.
Flexibility
and
strength
Adhesives
display varying degrees
of
flexibility.
It
can
generally
be stated that
(1)
there is an inverse
relationship
between
flexibility
and film
strength
of
the adhesive-the
higher
the
strength,
the lower the
flexibility,
and
(2)
in most
cases-except, perhaps,
for
rigid
substrates-it is
appropriate
for the adhe-
sive to mimic the
flexibility
and
strength
of the sub-
strate. For
example, applications
in textile
conservation benefit from
very
flexible adhesives
and the concurrent lower
strength
is not an issue
given
the
typical
loads associated with textiles.
Semi-rigid
substrates such as wood benefit from
stronger
adhesives that are semi-flexible.
Rigid
sub-
strates such as ceramics also benefit from semi-flexi-
ble adhesives because
glassy
adhesives
dry
with
large
residual stresses and are
prone
to fail
by peel
or fracture. Thus most conservation
applications
benefit from flexible or semi-flexible adhesives.
Flexibility
was studied
by monitoring
the stress/
strain curve of the adhesive as it
aged.
These curves
gave
information on the modulus of
elasticity,
elon-
gation
at break and cohesive
(film)
tensile
strength.
Stress/strain
procedure
The
flexibility
of the adhesives was measured
using
a modified ASTM test method for tensile
properties
of
organic coatings [22].
The film
preparation pro-
cedure involved
pouring
each adhesive onto Teflon
(1996)
19-44
30
Adhesive
testing
I . i i. I i i i i i
...;O.. .....*.i..........
. ...
. .
s
I I I I I I I I i
, p
7
'I
-
I I i?i~'
?
,
?
.
,
,.
,
. I ~ ~ ~
,
! i I t
* Dark
Aging
0
Light Aging
T Value higher *
than indicated
I
I o
' a
- *
0
c
E
?
?
'
ZL"
-
I ' I t
n
.....o.. . . . . . . . . . . . . ? . . ^ . . ,'
.XSS
?
I
>
a 6 to . . o 0
<
P Lo o)U
Xf m
O
a Z
?
a o a a I O >
n -.O* 1-"
HOMt)Li.OLY Re CO QLMR
i n-
W
\om
a I
I
C
!
I
>
I I
"
I
AGING TIME (yearU ) - - a -
...... ...... ............ .................... . .... ....................... . ................. ......... ................... .
I I I I I I I
I I
I
i
HDMPOLYMERS COPOLYMERS
m m :
0
-
10 U] D
C.) LLJ
m
--
HOO OLYER3
C3 -M
O
i ~
--
]1
I I
III
I 1 i !
I! tI I I I I iIII ( I
N4 ADIIE WITH ADIIE IT DIIE
HOOPLYER C
O O YMR
Figure
3 Results
of
the stress/strain measurements
for
the P VA C adhesives
after two, three and
four years of
dark
aging
and one
year of light aging (see
Table 8
for data).
Tensile
strength
data are
represented
on the
upper graph, elongation
at break data on the middle
graph,
and modulus
of elasticity
data on the lower
graph.
Each cluster
an adhesive. Adhesive clusters are
grouped according
to chemical
composi-
tion
(see
Table
1).
Small arrows indicate that values were
higher
than
indicated,
since the
samples
extended
beyond
the limits
of
the Instron Tensile Tester.
release
paper
and
allowing
it to
dry.
To ensure uni-
form
thickness,
the Teflon release
paper
was
secured to
flat, level, glass plates
and the films were
laid
using
a Gardner Film
Applicator.
The initial
stress/strain curves of these films were taken after
one month of
drying
in the dark. The films were
divided into two
groups
for each of the two
aging
environments. Stress/strain curves were taken after
two and four
years
of dark
aging
and after one
year
of
light aging (no light-aging
data exist for the
acrylic adhesives).
For stress/strain
testing,
films were cut into
dumb-bell
shapes
with a NAEF Punch-Press Model
B No. 8364. This
precision
cutter
(ASTM
D
412,
Die
C)
avoids
nicking
or
cracking
the films. The
use of
dumb-bell-shaped
test
samples
avoids neck-
ing problems during
the extension. To facilitate cut-
ting,
brittle films were relaxed for a brief
period
with heat or with heat and
high humidity (30?C,
80%
RH). Tacky
or
pliable
films were frozen and
cut
immediately.
These
cutting
conditions were
assessed to be too brief to have
any
effect overall.
About 10
samples per
adhesive were cut. Film
thickness was measured at five
points along
the
gage length, using
a Federal Thickness
Gage.
Films
that varied in thickness
by
more than 10% of the
average
were discarded. The
samples
were then
pulled
in an Instron Tensile
Strength
Tester
(gage
length 33mm,
cross-head
speed
for brittle
samples
10mmmin-1, cross-head
speed
for extensible sam-
ples
50mmmin-1' 50N and 5KN load cells
used).
This test
gave
modulus of
elasticity, elongation
at
break and cohesive tensile film
strength.
Stress/strain results
Table 8 and
Figure
3 summarize the results for the
PVAC
adhesives,
while Table 9 and
Figure
4
pre-
(1996)
19-44
......... ...........
o
a.
Cv
u)
C_
l
a
m
:n
c
1
m
o
c
0
oC
0-
LiJ
a
0-
2
C)
3
3
-a
o
2
10
1
0.1
000
100
10
1
1000
100
10
1
0.1
Strong
Medium
Weak
Extensible
Inextensible
Glassy
Semi-
Flexible
Flexible
I I I I _ I I I I I I I I I I I I I I I I I
rII I I I I I I I I I I I I I
31
*..
.. ..... . . ... . ..t
Table 8 Results of the stress/strain measurements (tensile strength, elongation at break and modulus
of elasticity) on the
poly (vinyl acetate) adhesives
Adhesives Tensile strength (MPa) Elongation at break
(%) Modulus of elasticity (MPa)
Control Dark
aging Light Control Dark
aging Light Control Dark aging Light
aging aging
-
0
year
- 2
year
- 3
year
- 4
year
-I
year
- 0
year
- 2
year
~3
year
-
4
year
-1
year
- 0
year
-
2
year
-
3
year
-4
year
-1
year
AYAA 27.5 '28.9
-
30.4 '23.7 2.47 2.40 -
2.37 2.36 3059 3202
-
*3435 2664
AYAC '8.8 - - - -
'1.19 - -
.2165
- -
AYAF 27.5 *22.7
-
29.1 "*19.2 2.15 2.23 2.69 2.69 3674 *2776
-
*3333 *2430
AYAT 34.3 29.1
-
*26.1 *17.3 3.03 2.57
-
*2.16 2.69 3774 *3171
-
*3545 *2006
Beva 371 3.78 4.28
-
3.82 *4.45 841 902
-
607 b*251 58.1 *90.3
-
*91.6 *157
Bondfast 13.3 *29.6 -
*23.8 *24.6 448 b*20.9
-
*5.38 *4.97 1354 *2703
-
*3504 *3225
Bulldog Grip 20 Min 14.1 a15.5
-
*17.8 *19.4 416 *354
-
394 "*193 1127 '1519
-
*1977 *2074
Bulldog Grip R-2311 23.4 *14.8
-
*21.5 *26.1 '6.40 *43.1
-
*13.9 '10.2 4359 *2507 *3463 4077
CM BondM-2 7.86
- -
*20.6 -
1098 - -
*3.68
-
114
- -
*3251
-
CMBondM-3 '20.7 '21.8
-
19.8 20.2 '1.82 '3.08
-
*3.35 *3.88 3025 2656
-
3400 3149
Elmer's Carpenter's 35.7 34.5
-
*24.8 *24.6 b137 b64.0
-
'*4.92 *4.84 2626 2886
-
*3009 *3292
Elmer's Glue-All 13.9 12.8 - *23.2 *18.2 423 *328
-
b*97.9 b*144 984 *1428
-
*2462 *2010
Elvace No. 1874 '9.9 12.4 -
*13.9 *13.6 957 1050
-
890 932 104 162
-
*225 *242
Gaylord Magic Mend 14.3 *19.7
-
*20.1 *18.7 833 *518 -
*488 *688 305 *1056
-
*1528 *869
Jade No. 403 6.80 5.98 7.34 6.42 7.94 899 824 *712 756 756 '35.1 *51.7 *121 *72.4 *160
Jade No. 454 2.12 2.05 2.16 *2.33 *3.23 50.6 53.6 *21.2 *37.1 *28.6 181 *265 *330 *295 *564
Mowilith DM5 >0.704 > >0.296 >0.578 >0.678 -
>1597 > >475 >2063 >2092
-
'22.8 34.2 b17.6 b22.7
-
>3 Mowilith DM5 + DMC2 '2.12 2.81 - 2.85 1.51 '1330 1608
-
1430 753 b41.1 '83.3
-
'75.1 *96.2
t
Mowilith DMC2 7.30 *5.67 *5.73 6.81 7.73 664 *851 708 712 614 b305 '*199 "229 *127 *468
~"
Promacto A-1023 7.45 6.94
-
*5.43 7.45 1083 *761
-
*969 *731 123 *180
-
*92.2 *218
X' R-2258 3.74 3.32 3.34 3.38 3.18 1071 1098 974 976 894 '41.3 46.2 *62.1 *30.4 *68.7
Rabin's Mixture '0.92 *2.37
-
*6.10 -
'890 *155
-
b*144
-
b60.6 "*371
-
'*717
-
z
Sure-Grip Carpenter's 10.9 *30.6
-
*26.9 *28.3 274 *3.93
-
*4.63 *4.10 b1140 *2712
-
*3305 *3796
Sl I UHU All-Purpose Clear '21.1 - -
23.6 -
'172
- -
152
-
'1893
- -
2175
"s Vinac B-15 35.1 '*21.8
-
34.2 *43.2 3.44 '3.08
-
3.15 3.22 '3147 2536
-
3562 *4072
~.
Vinnapas Dispersion EP1 1.94 >2.31 '1.84 1.99 1.92 889
-
b1014 *1392 b948 b16.8 b10.0 *9.07 *7.32 *12.1
z Weldbond 9.4 9.9 - 10.9 11.4 614 *455 - 619 *431 b488 *852
-
'*248 *974
Values indicate the mean of 3-10 samples; Standard errors are < 10% except where indicated;
'
Indicates standard error of 11-15 %;
b
Indicates standard error > 15 %;' Indicates a
single measurement only;
*
Indicates
significant
difference from control
Adhesive testing at the Canadian Conservation Institute
Table 9 Results
of
the stress/strain measurements (tensile strength, elongation
at break and modulus
of elasticity)
on the
acrylic
adhesives
Adhesives Tensile
strength (MPa) Elongation
at break
(%)
Modulus
of elasticity (MPa)
Control Dark
aging
Control Dark
aging
Control Dark
aging
-0
year
-2
year
-4
year
-0
year
-2
year
-4
year
-0
year
-2
year
-4
year
Acryloid
B44S 6.99 *21.7 *16.2 261 b*28.8 *2.76 670 *1795 *1683
Acryloid
B-48S 27.1 *28.1 *25.6 b65.7 38.8 b39.0 1584 *1861 1629
Acryloid
B-66
- - 1.49
-
b.594
- -
b098
Acryloid
B-67 too brittle
- -- - - --
Acryloid
B-72 6.25 *11.9 *18.1 351 *221 b*133 501 *962 *1246
Acryloid
B-82 4.82 *9.15 *12.7 332 *219 *211 450 b884 *914
Acryloid
B-99 too brittle
-
Acryloid
C-10-LV b0.130
-
0a.227
b461
-
>914 b17.2-
b10.8
Acryloid
F-10 5.08 *4.52 *8.68 511 499 *344 204 *532 *354
Acryloid
NAD-10 8.03
-
*5.98
b151
-
*291 601
-
*352
Elvacite 2013 too brittle
-- - - -- -
Elvacite 2028 .96- - - 2.40 - - 1204
Lascaux 360 HV - - >0.202
- - >768
- -
bl.90
Pliantex b22.1 18.2 24.6 b136 177 215 185 145 *85.1
Rhoplex
AC-33
- 7.63
- - 1168
- -
28.3
Rhoplex
AC-73 too brittle - -- - - -
Rhoplex
AC-234
- -
5.18
- - 1437
- -
10.0
Rhoplex
AC-234+AC-73 8.07
-
6.46 a538
-
698 190- a*92.9
Rhoplex
AC-235
- -
5.54
- -
1040
- -
24.2
Rhoplex
LC-40 "0.574
-
>0.411 >2899
-
>1018 t2.23
-
1.31
Rhoplex
N-560
-
>0.0769
- - > >524
-
'0.70
Rhoplex
N-580
- -
>0.0811
- - > >601
-
0.40
Rhoplex
N-619 0.153
-
>0.0656 1193
-
> >492 b27.8 b*0.210
Rhoplex
N-1031 0.707
- >0.174 1871
-
> >514 b0.878
-
a1.10
a4.51 a0.514 >1.05 1595 b*393 > >494 b2.61 *12.7 a*7.07
Values indicate the mean of 2-10
samples;
Standard errors are <10%
except
where
indicated;
a Indicates standard error of
11-15%;
b
Indicates standard error > 15%;
*
Indicates
significant
difference from control
sent the
equivalent summary
for the
acrylic
adhe-
sives. In order to
interpret
the results to make
choices of flexible
adhesives,
it was first
necessary
to determine
ranges
of
flexibility
and
extensibility
for conservation
applications. Polymers
exhibit
three
regimes
of useful mechanical behaviour:
glassy, rubbery,
and the transition between the two.
For
purposes
of classification into more
general
terms such as
'flexible', 'extensible', etc.,
the follow-
ing
boundaries were drawn.
Modulus
of elasticity
For all
amorphous polymers, fully glassy
behaviour
gives
a modulus of 3000MPa
[23, p. 48]
and the
transition to
rubbery begins
at about 2000MPa [23,
figures 3.2, 3.4]
so 2000MPa was set as the bound-
ary
to semi-flexible behaviour. The
boundary
for
so-called flexible behaviour was based on a
percep-
tible benchmark. Common
plastics
such as
poly(vinyl chloride)
and low
density polyethene
fall
just
below 400MPa
(150-350MPa),
so this was set
as the
boundary
for flexible behaviour.
Elongation
at break
Extensibility
could arise either from
rubbery
behav-
iour or from ductile
plastic
behaviour.
Rubbery
behaviour
easily gives elongations
of 100% or more
and
plastic behaviour,
which
may
reach well over
100%, gives
about 20%
elongation [23, figure 3.5]
at
its onset. Therefore 20% was set as the
boundary
between 'extensible' and 'inextensible'.
Cohesive tensile
strength
'Strong'
was set to include not
only glassy
adhesives
showing
their intrinsic brittle
strength
of 60MPa
[23, p. 54]
but also some ductile adhesives down to
15MPa
strength.
'Weak' was reserved for those
materials below the
strength
of a
typical elastomer,
polyisobutylene,
2MPa
[23, figure 3.8].
'Weak'
would thus include
only polymers already entering
viscous flow behaviour over the course of a few
minutes. These
ranges
can be seen on the
right
in
Figures
3 and 4.
(1996)
19-44
33
I I I I I I I I I I I I I I-
. . ....
. .............. .......... ... ..
.
... . .... .. ........................ -....... ................. ..........
:
/t
*
t -
r i i i L I i i I i I [ e
I i ? I 1
; ..................... a~ .............~ ...................................?.
.
<
.........
-
T o l I1 N" " I,
I
-oz
1
0^
Z ,
.
0
z
-o -e x>
x -o X
?
X
m
- _0 o
t
-_
->
x
L
o:~, 0
o
0 0
;* ,ve
<
*
i
T
:
_C
:j
41
Pr 0
0= o
P I))
- 0 LI 0o
I
o-
O
AGING TIME **j
u
?I UoC
? J(year?) ~J
< < C
z
'6
-&
o
a
o
I
I
Ee
E
0-1o
ES METACRLATES
PEA/PMMA P
Strong
..............I.
Medium
Weak
Extensible
Inextensible
Glassy
Semi-
Flexible
Flexible
I Value higher than indicated
Figure 4 Results
of
the stress/strain measurements
for
the
acrylic
adhesives
after
two and
four years of
dark
aging (see
Table 9
for data). (Note
that no
light aging
data are
available.) Single points represent aging
data
after four years of
dark
aging (i.e., only
one measurement
taken).
Tensile
strength
data are
represented
on
the
upper graph, elongation
at break data on the middle
graph,
and modulus
of elasticity
data on the lower
graph.
Each cluster
of points (or
a
single point) represents
an adhesive. Adhesive clusters are
grouped
accord-
ing
to chemical
composition (see
Table
2).
Small arrows indicate that values were
higher
than
indicated,
since
the
samples
extended
beyond
the limits
of
the Instron Tensile Tester.
Stress/strain discussion
The results of the stress/strain
experiments suggest
several
interesting
trends and features in the flexi-
bility
and
strength
of the PVAC and
acrylic
adhe-
sives. In
general,
the adhesives become less flexible
upon
dark
aging.
The PVAC adhesives
generally
possess
more
strength
and less
flexibility
than the
acrylics.
The stress/strain results of the PVAC adhesives
suggest
the
following general
trends:
(1) Predictably,
the PVAC
copolymers displayed
and retained more
flexibility
than the
homopolymers.
(2)
PVAC
copolymers, although
weaker than
homopolymers, displayed
sufficient
strength
for
most conservation
applications.
(3)
Also
predictably,
additives tended to increase
flexibility
and decrease
strength, especially
phthalate plasticizer.
The most flexible PVAC adhesives were Beva
371,
Elvace No.
1874, Gaylord Magic Mend,
Jade No.
403,
Mowilith
DM5,
Mowilith
DMC2,
Mowilith
DMC2 +
DM5,
Promacto
A-1023, R-2258,
Rabin's
Mixture,
Weldbond and
Vinnapas Dispersion
EP1.
The results of the
acrylic
stress/strain curves con-
firmed the
following general predictable
trends:
(1)
The
acrylates
tended to be more flexible and
weaker than the
methacrylates.
(2)
For the
butyl acrylate/methyl methacrylate
copolymers,
the
greater
the amount of
butyl
acrylate,
the more flexible and the weaker the
adhesive.
The
majority
of the
acrylic
adhesives
displayed
(1996)
19-44
J.L. Down,
M.A.
MacDonald,
0
Q-
, 10
Mu 1
C0v
0 c
1 0.1
(f
1000
100
0
m
._
1000
CT
0 1
1000
o
0
0)
:3
-0
0
2
100
10
1
0.1
* Dark
Aging
34
Adhesive
testing
0?~~~~.o
-~~~~~~~~~~~~~~25 1 1 1 1 1 1 1 1 1 1 1 1 1
iDiscoloration
Perceived
* Dark
Aged
Films
Perceived
0
Light Aged
Films
<a
n-
<0
0.20 -
c
0o
CD ,
0c .1 m
m ? 1 5u
c c 3 a
~0.1 5 U - c0 m-> a) a I c a I
I
$-
g?^ ?g- .|t^
?
O>
e< :s
o
E
? :
i ,
,o i
0.05~1$iLA; -s?S'X'>kS; i''.' CD 0 iS
AGING TiME (ye rs)
'
-
0
. 10
|
i?
r ii
11
NO ADDITIVES WITH ADDITIVES WITH ADDITIVES
Figure 5 Degree o yeong P C hived years of
dark and light aging (see Table 10 for data). Each cluster of points represents an adhesive. Adhesive clusters
are grouped according to chemical composition (see Table 1).
(
E I
0.05
I
. . .
I L
good flexibility,
with the
exception
of
Acryloid
B-
67, Acryloid B-99,
Elvacite 2013 and
Rhoplex
AC-
73,
which were too brittle to measure.
Yellowing
The
yellowing
of clear or colourless adhesives can
be an undesirable
property
for conservation
appli-
cations, especially
for
transparent
or
light-coloured
substrates. As
well, yellowing may
indicate instabil-
ity
or
degradation
of an adhesive. An adhesive that
remains clear and colourless or that
yellows
little
upon aging
is more suitable for some conservation
purposes.
To determine the resistance to
yellowing,
a
procedure
was followed similar to that
designed
for
epoxy
resin adhesive
testing.
The method is
described in detail elsewhere
[24, 25]
and is
only
briefly
outlined here.
Yellowing procedure
and results
Adhesives were
applied
with
microscope
slides as
thin films in
taped
wells to
acetone-degreased glass
slides. Five
replicate samples
were
prepared
for
each
aging
condition. Film
absorption
was mea-
sured
initially
at 380 and at 600nm on a Varian
2390 UV-VIS-NIR
spectrophotmeter equipped
with
an
integrating sphere
to
capture
all scattered
light.
Films were then
aged
in the two
aging
environ-
ments.
Samples
were removed at intervals
(six
months, one, two,
three and five
years)
and were
measured for
absorbance, again
at 380 and 600nm.
Degree
of
yellowing
(A)
at time
(t)
was calcu-
lated
using
the
following formula,
which subtracts
the
baseline,
absorbance at 600nm
[A(600)],
from
the ultraviolet
absorption
at 380nm
[A(380)]
and
standardizes the film thickness
(F)
to 0-lmm:
0 lmm
A =
[A(380)t
-
A(600),]
x
F
Tables 10 and 11
present
the calculated
yellowing
data for the PVAC and
acrylic adhesives, respec-
tively. Figures
5 and 6 show the
yellowing
curves
(1996)
19-44 35
Table 10 Results
of
the
yellowing
measurements on the
poly(vinyl acetate)
adhesives
Adhesives
Degree of yellowing [A,
=
(absorbance @ 380 nm - absorbance @ 600
nm)
*
(0.1
mm
/film thickness)]
Dark
aging Light aging
0
year
0.50
year
1.05
year
2.18
year
3.01
year
5.13
year
0
year
0.50
year
1.01
year
1.96
year
3.14
year
4.53
year
AYAA a0.0541 b0.0326 a0.0773 a0.0504 a0.0849 a.0610 b0.1015 b0.1071 bO.1257 bO.1334 b0.1975 b0.1331
AYAC b0.0493 a0.0499 aO.0688 b0.0441 aO.0728 aO.0501 0.0496 b0.0581 0.0583 0.0659 0.0927 0.0653
AYAF 0.0622 0.0603 0.0902 0.0582 0.0970 0.0627 0.0685 aO.0817 a0.0934 0.0932 ao. 1342 0.0880
AYAT b0.0592 b0.0605 b0.0878 b0.0582 b0.0953 b0.0659 0.0414 b0.0582 a0.0593 b0.0600 a0.0826 b0.0548
Beva 371 0.0434 a0.0463 0.0632 0.0649 ao.0733 0.0919 0.0425 0.1033 0.1329 0.1719 0.1760 0.1796
Bondfast 0.0338 0.0326 0.0429 0.0440 0.0479 0.0624 0.0333 0.0463 0.0472 0.0533 0.0456 0.0501
Bulldog Grip
20 Min 0.0713 0.0447 0.0556 0.0475 0.0516 0.0564 0.0739 0.0495 0.0558 0.0576 0.0568 0.0544
Bulldog Grip
R-2311 0.7136 0.6581 0.6792 0.6773 0.6848 0.6962 b0.6528 b0.6229 b0.6587 b0.6956 b0.7015 b0.6969
CM Bond M-2 0.0569 0.0557 0.0607 0.0521 0.0492 0.0562 0.0594 0.0552 0.0466 0.0520 0.0564 0.0507
CM Bond M-3 b0.1212 "0.0831 b0.1013 b0.0863 b0.0749 "0.0866 0.0959 0.0685 0.0668 0.0670 0.0640 0.0579
Elmer's
Carpenter's
0.1333 0.0804 0.0941 0.0823 0.0715 0.0938 0.1317 0.0908 0.0897 0.0943 0.0830 0.0890
Elmer's Glue-All 0.0608 0.0652 0.0830 0.0722 0.0763 0.0850 "0.0544 0.0521 0.0521 0.0626 0.0626 0.0583
Elvace No. 1874 0.0252 0.0270 0.0353 0.0314 0.0364 0.0336 0.0257 0.0290 0.0284 0.0327 0.0389 0.0344
Gaylord Magic
Mend 0.0433 0.0349 0.0497 0.0402 0.0433 0.0537 0.0491 0.0459 0.0474 0.0549 0.0620 0.0606
Jade No. 403 0.0381 0.0481 0.0544 0.0517 0.0539 0.0557 0.0342 0.0402 0.0418 0.0453 0.0509 0.0448
Jade No. 454 0.0911 0.0888 0.0925 0.0872 0.0910 0.1056 0.0809 0.0943 0.1046 0.1185 0.1231 0.1211
Mowilith DM5 0.0447 0.0612 0.0719 0.0683 0.0779 0.0834 0.0389 0.0448 0.0458 0.0541 0.0598 0.0539
Mowilith DM5 + DMC2 0.0309 0.0458 0.0540 0.0491 0.0557 0.0605 0.0253 0.0361 0.0376 0.0411 0.0510 0.0417
Mowilith DMC2 0.0317 a0.0404 0.0452 0.0365 0.0479 0.0476 0.0336 0.0425 0.0426 0.0444 0.0569 0.0444
Promacto A-1023 "0.0648 0.0677 0.0736 0.0582 0.0515 ao.0645 0.0680 b0.0826 "0.0884 a0.0992 0.0978 0.1142
R-2258 0.0235 0.0300 0.0351 0.0295 0.0348 0.0374 0.0245 0.0286 0.0333 0.0417 0.0498 0.0456
Rabin's Mixture 0.0217 0.0302 a0.0376 aO.0217 a0.0277 0.0331 b0.0229 b0.0330 b0.0412 b0.0429 b0.0573 b0.0402
0.0947 0.0883 0.1024 0.0938 0.0956 0.1153 0.1001 0.0974 0.0935 0.1037 0.0923 0.0939
UHU
All-Purpose
Clear 0.0187 0.0190 0.0279 0.0157 0.0193 0.0205 a0.0252 a0.0264 80.0306 80.0340 80.0487 0.0318
Vinac B-15* 0.0560 0.0777
-
0.0385 0.0494 0.0518 b0.0604 b0.0873 b0.0855 b0.1255
-
b0.0825
Vinnapas Dispersion
EP1 0.0313 0.0397 0.0493 0.0428 0.0486 0.0576 0.0309 0.0373 0.0392 0.0484 0.0585 0.0512
Weldbond 0.0324 0.0289 0.0332 0.0280 0.0301 0.0355 0.0285 0.0294 0.0323 0.0397 0.0396 0.0314
Values indicate the mean of 3-5
samples;
Standard deviations are < 15%
except
where
indicated;
a
Indicates standard deviation of 16-20%;
"
Indicates standard deviation >20%;
*
aging
times for this adhesive were: dark
aging
-
0, 0.55, 1.68, 2.52,
4.63
years; light aging
-
0, 0.50, 1.55, 2.73,
4.12
years
ZI
Zs
H.
-
t--
ti-
tz
Is
.
4c1
cpz
Q
Table 11 Results of the yellowing measurements on the acrylic
adhesives
I.
Adhesives Degree of yellowing [A,
=
(absorbance @ 380 nm -
absorbance @
600 nm)
*
(0.1 mm
/film thickness)]
Dark aging Light aging
0
year
0.50 year
1.05 year
2.18
year
3.01 year 4.64 year
0
year
0.50 year 1.01 year 1.96 year 3.13 year 4.53 year
z
Acryloid
B-44S 0.0390 0.0614 0.0754 0.0143 0.0263 0.0240 a0.0269 0.0375 80.0385 20.0230 0.0512 0.0325
0 Acryloid
B-48S 0.0169 bO.0170 a0.0244 0.0147 0.0176 0.0230 0.0188 0.0239 0.0221 0.0197 0.0386 0.0286
,-,
Acryloid B-66 b0.0299 b0.0396 b0.0598 a0.0296 bo.0504 b0.0478 0.0387 a0.0619 0.0690 0.0505 0.1011 0.0769
' Acryloid
B-67 b0.0091 "0.0128 a0.0187 a0.0122 a0.0189 a0.0178 0.0114 0.0184 0.0209 0.0162 0.0254 0.0172
,~ Acryloid
B-72 0.0286 a0.0343 0.0485 0.0238 0.0451 0.0380 '0.0330 0.0424 b0.0430 80.0482 '0.0728 '0.0538
L Acryloid B-82 0.0231 b0.0286 0.0410 0.0173 0.0359 0.0319 0.0343 0.0464 0.0427 0.0492 0.0786 0.0538
4
Acryloid
B-99 0.0200 0a.0288
- 0.0297 0.0315 0.0328 cracked films
- - - -
Acryloid C-10-LV b0.0247 b0.0409 b0.0550 bO.0376 b0.0470 b0.0536 bO0.0410 b0.0506 b0.0745 b0.0998 b0.1185 b0.1053
Acryloid
F-10 0.0254 0.0404 0.0543 0.0377 0.0491 0.0507 0.0344 b0.0562 0.0559 0.0538 0.0940 0.0783
Acryloid NAD10 b0.0494 80.0479 bo.0747 b0.0471 b0.0571 b0.0606 0.0352 a0.0415 0.0496 a0.0551 0.0664 0.0482
Elvacite 2013 b0.0367 b0.0608 b0.0814 b0.0554 b0.0718 b0.0712 cracked films
- - - -
Elvacite 2028 0.0290 a0.0351 0.0503 0.0280 0.0348 0.0376 0.0251 0.0354 0.0398 0.0261 0.0540 0.0361
Lascaux 360 HV 0.0164 0.0252 0.0311 0.0261 b0.0326 0.0336 0.0180 0.0266 0.0263 0.0294 0.0361 0.0326
Pliantex b0.0336 a0.0555 a0.0734 a0.0464 a0.0593 a0.0593 0.0208 0.0341 0.0322 0.0419 0.0508 0.0379
Rhoplex
AC-33 0.0183 b0.0365 0.0462 0.0388 0.0411 0.0495 0.0207 0.0381 0.0382 0.0341 0.0484 0.0390
Rhoplex
AC-73 too brittle
- - - - - - - - - -
Rhoplex
AC-234 0.0316 0.0472 0.0622 0.0482 0.0525 0.0643 0.0318 a0.0474 0.0475 0.0500 0.0627 0.0484
Rhoplex AC-234+AC-73 0.0256 0.0484 0.0580 0.0457 0.0570 0.0646 0.0254 0.0445 0.0493 0.0413 0.0594 0.0461
Rhoplex
AC-235 0.0184 0.0382 0.0487 0.0374 0.0431 0.0492 0.0215 a0.0458 0.0493 0.0410 0.0627 0.0526
Rhoplex
LC-40 0.0216 a0.0324 0.0405 0.0294 0.0334 0.0411 0.0246 0.0341 0.0394 0.0363 0.0551 0.0490
Rhoplex
N-560 0.0276 0.0439 0.0542 0.0409 0.0465 0.0547 0.0256 0.0361 0.0403 0.0524 0.0610 0.0541
Rhoplex
N-580 b0.0386 a0.0508 b0.0632 0.0484 0.0543 0.0683 0.0381 0.0473 0.0503 0.0663 0.0812 0.0703
Rhoplex
N-619 0.0179 a0.0294 0.0407 0.0293 0.0397 0.0447 0.0181 0.0350 0.0393 0.0497 0.0577 0.0534
Rhoplex N-1031 0.0435 0.0564 0.0679 0.0566 0.0631 0.0647 0.0461 0.0527 0.0557 0.0503 0.0678 0.0597
"0.0630 b0.1040 b0.1205 b"0.0790 b0.0977 b"0.0987 0.0910 0.1262 0.1257 0.1272 0.1871 0.1688
(film)
0.0813 0.1222 - b"0.0861 a0.0947 b0.1167 a0.1094 a0.1357 0.1110
- -
a0.1856
(toluene cast)*
Values indicate the mean of 3-5 samples;
Standard deviations are <15%
except
where indicated;
a
Indicates standard deviation of 16-20%; bIndicates standard deviation
>20%;
*
aging times for this adhesive were: dark
aging
-
0, 0.55, 1.68, 2.52, 4.08
years; light aging
-
0, 0.50, 1.46, 4
years
J.L. Down,
M.A. MacDonald, J. Tetreault and R.S. Williams
Strong
Discoloration
Perceived
Visible
Discoloration
Perceived
Figure
6
Degree of yellowing
(A,)
for
the
acrylic
adhesives
after
six months, one, two, three
andfive years of
dark and
light aging (see
Table 11
for data).
Each cluster
an adhesive. Adhesive clusters
are
grouped according
to chemical
composition (see
Table
2).
for each
adhesive,
and
plot average
At
with time
(t).
Lines are marked on the
figures
at
A,
=
0.1,
the
degree
of
yellowing
where a 0-1mm film would be
perceived
to be
visibly yellow,
and at
At
-
0.25,
the
point
at which the film would be
perceived
to be
strongly yellow [24].
Yellowing
discussion
Normally,
the
yellowing
curves would be
extrapo-
lated to
At
=
0-1 and 0-25 to determine how
long
it
would take a film to reach these
degrees
of
yellow-
ing. However,
to
date,
the
yellowing
curves have
not
yet fully developed
to the
point
that this can be
done with
any certainty. Nonetheless,
some trends
can be identified. In
general,
the PVAC adhesives
twice as
quickly
as the
acrylic
adhesives.
Light aging
tended to make all
the adhesives
yellow
more
quickly
than dark
aging.
As
yet,
no obvious differences in
yellowing
between
homopolymers
and
copolymers
have
emerged.
The
following
PVAC adhesives
displayed
the best
resistance to
yellowing
(all
A,
values <0.05; the dot-
ted line in the
figures):
Elvace No.
1874, R-2258,
UHU
All-Purpose
Clear Adhesive and Weldbond.
The
following
adhesives
displayed
fair resistance
to
yellowing
(all
At
values
<0.1): AYAC, AYAT,
Bondfast, Bulldog Grip
20 Minute
Resin,
CM
Bond
M-2,
Elmer's
Glue-All, Gaylord Magic
Mend,
Jade No.
403,
Mowilith
DM5,
Mowilith
DM5 + Mowilith
DMC2,
Mowilith
DMC2,
Rabin's Mixture and
Vinnapas Dispersion
EP1.
The
following acrylic
adhesives
displayed
the best
resistance to
yellowing
(all
At
values
<0.5):
Acryloid B-48S, Acryloid B-67, Acryloid B-99,
Lascaux 360 HV and
Rhoplex
AC-33.
The
following acrylic
adhesives
displayed
fair
resistance to
yellowing (all
At
values
<0-1):
Acryloid F-10, Acryloid NAD-10,
Elvacite
2013,
Elavacite
2028, Pliantex, Rhoplex AC-234, Rhoplex
AC-234 +
Rhoplex AC-73, Rhoplex AC-235,
Rhoplex LC-40, Rhoplex N-560, Rhoplex N-580,
Rhoplex
N-619 and
Rhoplex
N-1031.
(1996)
19-44
0.25
0.20
0 |
0.15
a)
0.05
0.00
38
Adhesive
testing
General discussion
In order to
compare
one adhesive to another
easily,
the results from the
pH, volatiles, strength, flexibility
and
yellowing
tests were tabulated
together.
Tables
12 and 13 list these results for the PVAC and
acrylic
adhesives, respectively.
The worst value for each of
the
aging conditions,
for each
adhesive,
for each
test,
is shown on these tables.
According
to these
tables,
the best PVAC adhesives were Jade No.
403,
Beva
371,
Mowilith DMC2 and R-2258. Also
performing
well were Rabin's Mixture and Elvace No. 1874. The
best
acrylic
adhesives were
Acryloid B-82, Acryloid
F-10, Rhoplex AC-33, Rhoplex AC-235, Acryloid
B-
72, Rhoplex
AC-234 and
Rhoplex
AC-234 + AC-73.
Also
performing
well were Lascaux 360
HV,
Acryloid B-44S, Acryloid NAD-10,
Elvacite
2028,
Rhoplex N-560, Rhoplex N-580, Rhoplex
N-1031
and
Rhoplex
N-619.
This
study
has
helped
to
identify
several adhe-
sives with
good pH,
volatile
emission, flexibility,
strength
and
yellowing properties. However, only
five
years-in
some cases less-of
aging
under mod-
erate conditions were studied. The results must be
viewed with this limitation in mind.
Some valuable lessons were learned that could
benefit others
attempting
a
project
of similar
nature.
Testing
fewer
products
would have
expe-
dited the
project. Perhaps
if fewer
products
were
tested then more
properties (i.e., removability,
shrinkage, gloss, etc.)
could be examined.
Therefore,
in
future,
it would seem
prudent
to use a
pH screening
test to reduce still further the number
of
products
tested.
Conclusions
Tests carried out on PVAC and
acrylic
adhesives
have identified several adhesives with
good pH,
volatile
emission, flexibility, strength
and
yellowing
properties.
From this
study,
the
following general
conclusions can be drawn:
(1)
The
pH
results showed that the PVAC adhe-
sives were more acidic than the
acrylic
adhe-
sives and that
light aging
tended to decrease
pH
of both classes. The PVAC
homopolymers
were
generally
more acidic than the PVAC
copoly-
mers,
and
many acrylic
adhesives
containing
butyl acrylate
were found to be neutral.
(2)
The
analysis
of volatile
compounds
from the
PVAC and
acrylic
adhesives showed that
they
emitted various ester and residual solvent com-
pounds. Only
the PVAC adhesives released
appreciable quantities
of acetic acid but
any
risk associated with these emissions decreases
rapidly
after the initial
curing period
of several
weeks.
(3)
In
general,
both the PVAC and
acrylic
adhe-
sives became less flexible
upon
dark
aging,
and
the PVAC adhesives were
stronger
and less flex-
ible than the
acrylic
adhesives. PVAC
copoly-
mers
displayed
and retained more
flexibility
than the PVAC
homopolymers.
(4)
The PVAC adhesives
twice as
quickly
as the
acrylic
adhesives and
light aging
tended to make all the adhesives
yel-
low more
quickly
than dark
aging.
(5)
This research has identified
groups
within the
PVAC and
acrylic
classes
(e.g., vinyl/acetate
ethylene copolymers
and
butyl acrylate copoly-
mers)
with
good properties.
This
suggests
that a
more
in-depth
look at these
groups
is war-
ranted.
Although
it is
hoped
that this
study
will assist con-
servators in
making appropriate
adhesive
choices,
it
must be
emphasized
that each conservation
applica-
tion is
unique
and other concerns such as remov-
ability, shrinkage, gloss,
bond
strength,
adhesive/
substrate
interactions, etc.,
which were not exam-
ined in this
study, may
also be
important.
Each
individual case must be
carefully
assessed before an
adhesive is selected.
Acknowledgements
The authors
sincerely
thank and
acknowledge
each
of the
following people
for their valued efforts:
France
Bertrand,
Mona
Gudgurgis
and Deb
Bisaillion for their technical assistance with the
pH
and
yellowing measurements;
Mark
Boyle
and
David Miller for their technical assistance and
advice on the volatile emission
measurements;
Helen
Burgess
for her advice
concerning pH
and
the
acceptability ranges
for
paper;
Stefan Michalski
for his advice on the stress/strain
experiments;
Dr
David McLean for his
expertise
in the statistical
analysis
of the stress/strain
data;
Paul Marcon for
his assistance with the data
aquisition
control mod-
ule for
measuring
film thickness for
yellowing;
Tom
Strang
for
computer
assistance and
programming;
and Charles
Costain,
David
Grattan,
Ela
Keyserlingk
and
Ray
Lafontaine for their advice
and constant
support
on all
aspects
of the
project.
Materials and
suppliers
Acryloid B-44S, B-48S, B-66, B-67, B-72, B-82,
B-
99, C-O1LV, F-10, NAD-10: Rohm & Haas
(1996)
19-44 39
J.L. Down, M.A. MacDonald, J. Tetreault and R.S. Williams
Table 12 Overall performance of the poly(vinyl acetate) adhesives
Adhesive pH Volatiles Tensile strength Flexibility Yellowing
0 D L D L 0 D L 0 D L 0 D L
Vinyl acetate homopolymers
AYAA ..............S S B B B P f P
AYAC A . A -B
-f'......f......... ..
AYAF A N A I I S S S B B B f f P
AYAT A
lsi
s A Ig S S S B B B f f f
..........................
::::::::::::::::
Vinac B-15 A N A I I S S S B B B f f P
Sure-Grip Carpenter's A A A m h M S S R B B P P P
UHU
All-Purpose
Clear A A A
iiiiiiii i
..S S
- is.:
B
-
i
Rabin's Mixture A
-
I W M. f
CMBondM-2 A A A h h M S F B f f f
CM Bond M-3 A A A m m S S S B B B P P f
Promacto A-1023 A A A I m M : F F F f f P
Elmer's Glue-All A A A m m M S S F. B B f f f
Weldbond A A A m m M M F P G
Bondfast A A A m
h
S S B B f f
Gaylord Magic Mend A A
Ai
iii
m S S
PiiU~ii?
f f
Bulldog Grip 2311
A A A I m S S S B B B P P P
:.....ii.:iiiiii.iiiiiiii......
Bulldog Grip
20
Min A A A m m S S .......... B f f f
Elmer's Carpenter's A A A m m S S S B B B P f f
Vinyl acetate / ethylene copolymers
Jade No.454 A A A m f P P
Elvace No. 1874m
Vinnapas Dispersion EP1 A A m I W W W
.
f f
Beva 37l ~ N 1N I M M F F..
.
.
f P
.. . .. . . . .. . . .. . . . . . . .. . .. . ..
.
.. . . .. . .. . .. . i:i:::::::::j::j::::j:::jj:::i:::j::::: ??:?:?:?:.5:?:'.:t.i:.. ::j:i.~::::::::~:~~: .................:
:::i:s;~s;~;~;::~::~~3:::W :~::
. ..........
~ :.
.....
.......:~:~: .1?: ;:f.:?:.:.:?f: ?~~~~~~~~?:.:.: ?~~~~?:?:?:.:-:?15:~~~~~~~~: ?.?.?rr:
:: ~ ~ ~
.......
W eldbond
....... .. .......
............
...i~ ~ ~~.~:~:d c~~:;:::~;?i :~~ii~~~~ii~~j ?~~??,:? m ~ ~ ~ ~iiiii.
. . . . ......... .. .............
:i~~:~~::::~~~::~~:~:l~~?:.... ................................. ....
.
...................
Elmer's
Capenter's
A A A m m s S B B B f f
Vinyl
acetate
ethylene copolymers~~~~~~~?:?:~:~:~:~:~:~~:~::::::~
?~?~::::'f::~:~~: ?~?:::~~:: ? ~ :~~:~~::~:~::~~:~:~:::::i::.:i::~.:.:. .. . ..:~j~;:
Jade N o.454 A A A m h
..... .
..... . .....
........
.
......:~~:~:~::~~::~:::~::~' ~ ~ ~ i ~ i: ; ?
Beva 371 :~:?:~s:~:i~:~:~::::iii~i~i~i~t?Ej~i j:c :?:~::~::;::! ~?:?~s?~st :;I:.......... ... .. ............ ?
iiiiiii~~~i~~.T:~:~~.:4~:~~~ii::;;?1??r?:??:?:r;??t?I????c?I?:r; .: :::~:,, i:::~1?~:11)1:2.: ....::::
... ..... ......... . 77.
t0:.~?~5 r-?~?~?X?:?~;::R;:;:; ? ?f~5s ;.
. . . .... . . ...... .... .
......?~i
Vinyl
acetate /
acrylic copolymer
Mowilith DM5 A A A m m W W - -
ii
f f
Vinyl
acetate / maleate
copolymer
Mowilith DMC2, m m ji..j.G f
Vinyl
acetate /
acrylic
/ maleate
copolymer
MowilithDM5 + DMC2 : .::...:: h h
i iiii:i
W
i
if
f
0 = 0
years;
D =
dark
aging;
L
=
light aging;
For each of the
above,
the worst value of the entire
aging period
was taken;
pH (dry
film extracts
only)
-
A
=
acidic
(pH<5.5);
N
=
neutral
(pH=5.5-8.0);
AL
=
alkaline
(>pH=8.0);
Volatiles
-
1
= <
1IAg
acetic acid /
g adhesive; m = 1-10
.tg/g;
h = > 10
tg/g;
Tensile
strength
- M
=
medium
strength (2-15 MPa);
W = weak (<2 MPa);
S =
strong (>15 MPa); Flexibility
- B
=
brittle
(elongation
<20% or modulus >2000
MPa);
F
=
flexible
(elongation
>20% or modulus <2000
MPa) Yellowing
-
G
=
good, A,
<
0.05; f =
fair, At
= 0.05 to 0.10;
P
=
poor, At
>
0.10; Shading indicates desirable
properties.
(1996)
19-44 40
Adhesive testing at the Canadian Conservation Institute
Table 13 Overall
performance of
the
acrylic
adhesives
Adhesive pH Volatiles Tensile
strength Flexibility Yellowing
0 D L D L 0 D 0 D 0 D L
Homopolymers
Acryloid
C-10-LV A
A aa Wi
Rhoplex LC-40 A A A D
R:&.f&L
W W
Rhoplex
N-580 Xafamaaa a {Ni 2 > W - a f f
*:'. , ---. ... R.RR... -,R '.. ....... 'R'R'-'
~~~~~~~~~~..Elvaci...-"te 2028 '.fi-- .R '' ' 2- - tR*ji~i~~jiS~ '>'-',Q ::I::'--'1::::~:I::. . .. ..._ f
Acryloid F- 10 * -@- - X -- Re-0-6>-e se. i R R R R R R.R
.........,..., .....r ...:........... ...,..
..........................
Acryloid B-67 "w? R*. -"RR-R i
...:-'
. ..
nr':
.
....:.......
.
.:R:-::-::-:.:..:- ::: :
. .
CODOIVMerS. .. .
...... .... ......
?:?:?:?5?:?:?:?::?:?:?:?f.........
. ... .. .... . .i:?.l.??l.??.?..................
ii~i~i tj~i~ E~ii~'"'' ~ ?'::"'::::::"':::::";'
""" .:. ...... .. .......
Elvacite 2028 ""' ...~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~0.......
............... .... ... .. ...........Jr.: ....
? ;V: ? ;??
.
??.....................?.?. ??.??.?..?..?..?.??. .........????
................ ......... ...... .....??....,.,?:::.r ??????.::::. cs:s
............ ??????????. ?????? ....... :??I?::?.?.::.?.3.?:i':
....... ..
..............~~~iijii
...... X::5
?II:: ???::~: ????: ?
.......
............. ................ ~ i~~.~'..'~~.~ .......~~~...s.~ ~ ;~:. ~ ;s..~ s ,.s;~;; ~i; ~5;si
.
...........................r ?.. ., '? ? ?? ??" .....
... ....... . ..
.......:c??I??II???:?:::??:::??:.... . .. ,, .
.....
.
.
.... ..
....?'. ??. ... :.
A
cryloid
F -10 ii~Siiiiiiji'' iiiiiii~iiiiiii~iiji~jijiii~t~iitiE tiMiiiSi:tiiiB
B iii
jS~..........
f fi~~iiiii
?????. ??:??? ;::.?::?::??::??? ?::? .............?? ?????i??)??
Conol~vmers9
Acryloid
B-72
N.....il
A i
MS f. .
:::::::~~~~~~~~:~~~S~~::-:il~~~~~~~~~: i?R:?:s?: ? ?.?.?.?.?.?.?.?u ? :?:5 L
~ ~ ~ ~ ~ ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: .....
...........
............ ........ . ..?.?.s?.?.?.?.?.?.?.?;:?.?.?.?;?.?.?;?.................is:!i:::?ii:::?is:i:i
}
R.hoplexAC-234 Nlii~-~ iii A A i!iii?i?iil}~i~i:i!i~ii: A n! n M! F G: fiii f!i ~iiii?:.~iii!iiiii:!i~.i~:iii~:i!~~.i!!i!Mi:j:i~ii:
.:?:?:?: .......??:?: 1 '::'":::'?::
':::......:':'......:....ii:
~~~~~~~......
....::.......
.-
...
. . . .
f f
i::i::j:3?::i:~i::i:: ii A
I: ???? ?' A~ il}iiii!?::?:.::
:???
RhoplexNAC-..3 N?:.."
A A i!:i:
...
..B
......B.
.............
v. . ...... ;.:-..v.....v.
Acrupported8 T e NiNr yN - A AMiMiF FiU::i!G!!ifif::::::!iii!ii!! W P P
?~:?:?u;+I::............... .::: : : : :::::::::::::::::::::::::::::::::::::: ::::::::::::::::::::::
RhoplexNA-234
N NC7
Nii?-i:~i?
A Ai W W:: F::::: F
Giii?i ?$?::!!f:
.......:.......:....
.
..:::j.. f
RhoplexAC-235
Niii?i::i
A A
!iii-iFiiGii!if:
fi!iii!iiiiiii!iiiii:~~5~
RhoplexN-560~~~~~~~:5:::?:??:I N?????:::??:: ???????? N N .??.?i
- W F
..?.. ?
f
f?
Elvaite2l3 N N n - - B B - f
AcryloidB6 i
!i'iiiiiiiiii'iiiii:ii. . .. ..... .............. . . . . ..
RhoplexNC-033 N.......... .....Ni ....
R hoplex A C -23 5
:::~:~~i:::::: :.?:.::?:1. s?
??:?::?:?::?:.?:.:.Ij~~
?
.. ............. ....'i:
:
: . :. : .:.:.v....v... ..
Acryloid B-99 N N N ~ ~ ~ ~~~ ~~ ~~~~~~~~- - B B U}~liii~iiii f~ -
:: :
...... '
..........'
.... . ......
A A ........:}:!:l f
.:::
: : .::::::::::::
:
.............
.......
.....
...............
.............::;:i:5::;::i:;~::5;:si9. . ::...
Rhoplex AC-234s AC-73 aii:c .)A A nA:.....50 W
a :i::H: .0)
f f
Acryloid - 99 iiiii~!iii'iii!!?~iii}liiii'i$ii"?~}iiiiii!i!iiil}!?~i!!:'~'iii!} ...............................B..........
... ........
.. . . .....................
............
........
Rhoplex
AC-73
idic
( pH
<5.5); A A ( pH=5.5-8.0);B B
n = no dangerous volatiles released; 1 < ljxg acetic acid I g adhesive; Tensile strength - M = medium strength (2-15
MPa); W = weak (<2 MIPa); S = strong (> 15 MPa); Flexibility - B = brittle (elongation <20% or modulus >2000
MPa); F = flexible (elongation > 20% or modulus <2000 MPa) Yellowing - G = good,
At
< 0.05; f = fair,
At
= 0.05
to 0.10; P = poor,
At
> 0.10; Shading indicates desirable properties.
:::::~~~~~t:15:~~~~~C:. ?:?s~~~~~~~:tI: ? u ??. ??
. ... ..
:?:;:?.
?.... . ... . .i
A cryloid B
-44S
B f f~5:?:1%:::??????::::: ??:::.?:??????:"'' ??:?????~
I??O::
..........tS...... ... :::i::::::j:::i:1~::: :.?:.?:i?:~~~~~~?: .?.~~~~r?.~ ~? ..... ...........
. ..........::::? S:?;?';? .:::
Rhoplex
N-619 W f~~~~~~~~ ????????..?.. ??.??-..???
Acryloid B-48S A A A ::s :
????:s~?~?:???????:???~.?:s?:::
:? ::::l???
.;?::::
::???~
?
:~?::::;~.::~:~:::::~.:::::::::: ~ ""'" """" '?'' ,:?:'':. . . ............. ?.?. ? ..
.. ?? ???,. ??....... ..... ...
..
..
?:??.'.:;f%::i~~i : ? ?
Rhoplex
AC-235 A A~.:ii?S?:i:;i:;?$: ::C:;.:).
....................~~~~~~~~~~~~~~~~~.::~~~.
;?'.
. ..................... .........
~ ~ ~ ~ ~ ~ ~ ~ ~ ?c:.?..::2.:.?:.r.:::~~:::
Rhoplex
N-560
f
f~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~i:;::::::::;::;-::?:::::x:?::?:::
A
cryloid B-66S A
A
iB f p?:?
SS?:::';??
;:::.????
.........?: ?.. ??...?.?.. ...... .. ... . .........''''''''
Rhoplex N-131W
........... .
f
...... ....
.~~???l?.? ..;?'.- ??:::::::: ?:???
Acryloid
B-99
B
B:.:::::: ::X.?O::X:L5?\??..
C:1:??:::~?;?f3~::I
Acryloid
NAD-10 A A f
f~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~?:Z:::???.\;~:.???::::
0 =0
yars
D= drk
gig;
=
igt aing
Fo ech f te
bov,
te ors vaue f he ntie
gin peio
wa taen
pH (dy
fim exract
only
-
A= acdic
pH <5.5);N
=
eutrl
(p=
5.58.
0;
AL= alalin
(pH=> 8.0);
olatles
n
=
no
dangerous
volatiles released;
I
=
<
lAg
acetic acid/
g adhesive;
Tensile
strength
-
M
=
medium
strength (2-1
MN);
W
=
weak
(<
2
MN);
S
=
strong (>
15
MN); Flexibffity
-
B
=
brittle
(elongation
< 20 % or modulus >
2000ss:.:t?:?:?:C?:
MPa);
F
=
flexible
(elongation
> 20 % or modulus < 2000
MPa) Yellowing
-
G
=
good, At
< 0.
05;
f
=
fair, A.
=
0. 05~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~:??::?::?::??:??f:: ??:??:??:
to 0. 1
0;
P
=
poor, At
> 0. 1
0; Shading
indicates de::?~?:?:sirabl prpertes
(1996)
19-44
......
41
J.L. Down. M.A. MacDonald. J. Tetreault and R.S. Williams
Canada
Inc.,
2 Manse
Road,
West
Hill,
Ontario,
Canada M1E 3T9.
AYAA, AYAC, AYAF,
AYAT: Union Carbide
Canada
Ltd,
1000 Finch Avenue
West,
Downsview, Ontario,
Canada M3J 2E7.
Beva 371:
Sigmund Haller,
Bank of Nova Scotia
Chambers,
79
Queen Street, Toronto, Ontario,
Canada M5C 1R8.
Bondfast:
Lepage's Ltd,
50 West
Drive, Bramalea,
Ontario,
Canada L6T
2J4,
Canada.
Bulldog Grip
20 Minute
Resin, Bulldog Grip
Resin
2311: Canadian Adhesives
Ltd,
81 Kelfield
Street,
Unit
7, Rexdale, Ontario,
Canada M9W
5A3.
CM Bond
M-2,
CM Bond M-3: Conservation
Materials
Ltd,
Box
2884,
340
Freeport
Boulevard, Sparks,
NV
89431,
USA.
Elmer's
Glue-All,
Elmer's
Carpenter's
Glue: Borden
Chemical
Canada,
595 Coronation
Drive,
West
Hill, Ontario,
Canada M1E 4R9.
Elvace No. 1874:
Talas,
Technical
Library
Services
Inc.,
213 West 35th
Street,
New
York,
NY
10001-1996,
USA.
Elvacite
2013,
Elvacite 2028: Du Pont Canada
Inc.,
PO Box
26,
Toronto Dominion
Centre,
Toronto, Ontario,
Canada M5K 1B6.
Gaylord Magic-Mend: Gaylord Library Supplies
&
Equipment,
PO Box
4901, Syracuse,
NY
13221-4901,
USA.
Jade No.
403,
Jade No. 454:
Talas,
as above.
Lascaux 360 HV: Lascaux
Farbenfabrik,
Riedmuhlestrasse
19,
8306
Briittisellen,
Switzerland.
Mowilith
DMC2,
Mowilith DM5: Hoechst Canada
Inc.,
4045 Cote Vertue
Boulevard, Montreal,
Quebec,
Canada H4R 1R6.
Pliantex:
Originally
obtained from Frank W. Joel
Ltd,
but no
longer
available.
Promacto A-1023:
Talas,
as above.
R-2258:
Talas,
as above.
Rabin's Mixture:
50g
AYAA and
50g
AYAC dis-
solved in 154ml toluene
(methylbenzene)
to
which 12ml of Multiwax solution
(2g
Multiwax
No. 445 melted in 25ml
toluene)
is added.
Rhoplex AC-33, AC-73, AC-234, AC-235, LC-40,
.N-560, N-580, N-619,
N-1031: Rohm & Haas
Canada
Inc.,
as above.
Glue:
Lepage's Ltd,
as
above.
UHU
All-Purpose
Clear Adhesive:
Talas,
as above.
Unsupported Texicryl:
Lisle Kelco
Ltd,
6799 Steeles
Avenue
West, Rexdale, Ontario,
Canada M9V
4R9.
Vinac B-15: St Lawrence Chemical
Inc.,
5405 Pare
Street, Montreal, Quebec,
Canada H4P 1P7.
Vinnapas Dispersion
EP1:
Henley
Chemicals
Ltd,
1735
Bayly Street, Pickering,
Canada L1W 3G7.
Weldbond: Frank T. Ross & Sons
(1962) Ltd,
PO
Box
248,
West
Hill, Ontario,
Canada M1E
4R5.
References
1
DOWN, J.L.,
'Adhesive
testing
at the Canadian
Conservation
Institute, past
and future' in
Adhesives and
Consolidants, IIC,
London
(1984)
18-21.
2
DOWN, J.L.,
and
WILLIAMS, R.S.,
'A
report
on
the evaluation of selected
poly(vinyl acetate)
and
acrylic
adhesives for use in
paper
conser-
vation' in Conservation
of
Historic and
Artistic Works on
Paper, Proceedings
of
Symposium 88,
Ottawa
(1994)
163-180.
3
DOWN, J.L., MACDONALD, M.A., TITREAULT,
J.,
and
WILLIAMS, R.S.,
'Adhesive
testing
at
the Canadian Conservation Institute-an eval-
uation of selected
poly(vinyl acetate)
and
acrylic
adhesives', Environment and Deterio-
ration Research
Report
No.
1603,
Canadian
Conservation
Institute,
Ottawa
(1992).
4 'Standard test method for
hydrogen
ion con-
centration of
dry
adhesive
films,
D
1583-61',
Annual Book
of
ASTM Standards 22
(1982)
477-478.
5
BLACKSHAW, S.M.,
and
DANIELS, V.D.,
'The
testing
of materials for use in
storage
and
display
in museums', The Conservator 3
(1979)
16-19.
6
BRADLEY, S.M.,
'Safe fabrics for
permanent
exhibitions',
Conservation News 23
(1984)
16-18.
7
BARROW, W.J., Manuscripts
and
Documents.
Their Deterioration and Restoration,
2nd
edn,
University
of
Virginia Press, Charlottesville,
VA
(1972)
45-47.
8
BARROW, W.J.,
The
Manufacture
and
Testing of
Durable Book
Papers, Virginia
State
Library,
Richmond,
VA
(1960)
14.
9
WILHELM, H.,
and
BROWER, C.,
The
Permanence and Care
of
Color
Photographs:
Traditional and
Digital
Color
Prints, Color
Negatives, Slides, and Motion
Pictures,
Preservation
Publishing Company, Grinell,
IA
(1993)
470-472.
10
BURGESS, H.D.,
'Other cellulosic materials' in
Storage of
Natural
History
Collections: A
Preventive Conservation
Approach,
ed. C.
ROSE and C.
HAWKS, Society
for the
Preservation of Natural
History
Collections
(1995)
291-302.
11 American National Standard
for Information
Sciences-Permanence
of Paper for
Printed
Library
Materials, ANSI
Z39.48-1984,
(1996)
19-44 42
Adhesive
testing
American National Standards
Institute, Inc.,
New York
(1984).
12
FARMER, R.H.,
'Corrosion of metals in associa-
tion with wood. Part 2. Corrosion of metals
in contact with
wood',
Wood
(November
1962)
443-446.
13 'Corrosion of metals
by wood',
Guides to
Practical Corrosion
Control, Department
of
Industry,
London
(1980).
14 American National Standard
for Imaging
Media-Photographic
Processed
Films,
Plates,
and
Papers-Filing
Enclosures and
Storage Containers,
ANSI
IT9.2-1991,
American National Standards
Institute, Inc.,
New York
(1991).
15
REILLY, J.M.,
'Role of the
Maillard,
or
"pro-
tein-sugar"
reaction in
highlight yellowing
of
albumen
photographic prints'
in
Preprints of
Papers
Presented at the Tenth Annual
Meeting, Milwaukee, Wisconsin,
American
Institute for
Conservation, Washington,
DC
(1992)
160-168.
16
EASTOE, J.E., 'Composition
of
collagen
and
allied
proteins'
in Treatise on
Collagen,
Vol.
1, Chemistry of Collagen,
ed. G.N.
RAMACHADRAN,
Academic
Press,
London
(1967).
17
MARCH, J.,
Advanced
Organic Chemistry,
Reactions, Mechanisms,
and
Structure,
John
Wiley
&
Sons,
New York
(1968)
334.
18
MIDDLEDITCH, B.S., Analytical Artifacts, GC,
MS, HPLC, TLC and
PC,
Elsevier Science
Publishers,
Amsterdam
(1989)
343.
19
CLARKE, S.G.,
and
LONGHURST, E.E.,
'The
corrosion of metals
by
acid
vapours
from
wood', Journal
of Applied Chemistry
11
(1961)
435-443.
20
TETREAULT, J.,
'Corrosion of
copper,
zinc and
lead in acetic acid
vapour', unpublished
work,
Canadian Conservation Institute
(1992).
21
TITREAULT, J.,
'Evolution des
produits
volatils
liberes
par
des adhesifs PVAC at
acrylique',
Environment and Deterioration Research
Report
No.
1874,
Canadian Conservation
Institute
(1990).
22 'Standard test method for tensile
properties
of
organic coatings,
D
2370-82',
Annual Book
of
ASTM Standards 06.01
(1988)
331-334.
23
GIBSON, L.J.,
and
ASHBY, M.F.,
Cellular Solids
Structure and
Properties, Pergamon Press,
Oxford
(1989)
47-55.
24
DOWN, J.L.,
'The
yellowing
of
epoxy
resin
adhesives:
report
on natural dark
aging',
(1984)
63-76.
25
DOWN, J.L.,
'The
yellowing
of
epoxy
resin
adhesives:
report
on
high-intensity light
aging',
(1986)
159-170.
Authors
JANE L.
DOWN
graduated
from
Queen's University,
Kingston,
Ontario in 1973 with an Honours BSc in
chemistry
and mathematics. From 1973 to
1978,
she worked in various areas of scientific research
including
forensic science at the Ontario Provincial
Police
Laboratory
in
Toronto, biochemistry
at
Queen's University, pharmacology
at the
University
of Ottawa and
pesticide chemistry
at the
Chemistry
&
Biology
Research Institute at
Agriculture
Canada
in Ottawa. In
1978,
she
joined
the Canadian
Conservation Institute as a conservation scientist.
Her main area of concern is adhesive research.
Address: Canadian Conservation Institute,
Depart-
ment
of
Canadian
Heritage,
1030 Innes
Road,
Ottawa, Ontario, Canada KIA OM5.
MAUREEN A. MACDONALD studied
biochemistry
at
Algonquin College,
Ottawa. She worked on medical
research of viruses in the
Faculty
of
Medicine,
University
of Ottawa before
joining
the Canadian
Conservation Institute in 1981. Her research inter-
ests include environmental
monitoring equipment
and the deterioration of natural
history specimens.
Address: as
for
Down.
JEAN TETREAULT
graduated
in 1989 from the
University
of Montreal with a MSc in
analytical
chemistry.
In the same
year
he
joined
the Canadian
Conservation Institute where he is
currently
work-
ing
on the control of outdoor and indoor
pollutants
and their effects on artifacts. In addition to
research and
supervision,
he
gives many
seminars
on
preventive
conservation and on
display
and stor-
age materials,
both
nationally
and
internationally.
Address: as
for
Down.
SCOTT WILLIAMS obtained an Honours BSc in
chemistry
from the
University
of British Columbia
in
1971,
after which he worked for five
years
as an
analytical
chemist at the Canadian Customs &
Excise
Laboratory.
He
joined
the Canadian
Conservation Institute in 1977. Now in the
Conservation Processes Research Division of
CCI,
he continues his research on
plastic storage
materi-
als and extends this to the deterioration and conser-
vation treatment of museum
objects
made of
plastics.
Address: as
for
Down.
(1996)
19-44 43
J.L. Down, M.A. MacDonald, J. Tetreault and R.S. Williams
Resum&-En 1983, le Canadian Conservation Institute
(CCI)
entame un
programme
d'evaluation de 27
adhesifs
au
polyacetate
de
vinyle (PVAC)
et de 25
acryliques, pour
etudier leur
pH,
l'emission de
produits
volatils
nocifs,
leur
force
et leur
flexibilite,
et le
jaunissement apres
vieillissement a la lumiere et dans le noir.
Les mesures de
pH
ont montre
que
les
adhesifs
au PVAC sont
plus
acides
que
les
adhesifs acryliques
et
que
le
vieillissement d la lumiere tendait t
faire
decroitre les deux
pH.
Les
homopolymeres
au PVAC sont
generale-
ment
plus
acides
que
les
copolymeres
au PVAC et la
plupart
des
adhesifs acryliques
contenant de
l'acrylate
de
butyle
se sont reveles neutres.
L'analyse
des
composes
volatils des
adhesifs
au PVAC et
acryliques
a montre
qu'ils
emettent
differents
esters et des
composes
du solvant
residuel,
mais seuls les
adhesifs
au PVAC liberent
des
quantites
notables d'acide
acetique.
Les resultats ont
indique que, apres
une
periode
de remission de
plusieurs semaines, l'evolution de l'acide
acetique
des
adhesifs
au PVAC ne devrait
pas provoquer
des risques
majeurs.
En
general
les deux
adhesifs
au PVAC et
acryliques
sont devenus
moinsflexibles apres
vieillissement
dans le noir et les
adhesifs
au PVAC ont montre
plus
de resistance et moins de flexibilite que
les
acryliques.
Les
copolymeres
au PVAC
manifestent
et
gardent plus
de
flexibilite
que les homopolymeres
au PVAC. Les
adhesifs
au PVAC ont
jauni approximativement
deux
fois plus
vite
que
les
adhesifs acryliques,
et le vieillisse-
ment a la lumiere tend a
jaunir
tous les
adhesifs plus
vite
que
le vieillissement dans le noir. Les resultats de
chaque
test
pour chaque adhesif
sont
classifies
dans un tableau
qui fournit
une vue d'ensemble et
permet
d'e-
valuer les donnees.
Zusammenfassung-Im
Jahre 1983 setzte das Canadian Conservation Institute
(CCI)
ein
Forschungsprojekt
in
Gang,
um durch
Reihenuntersuchungen
an
Klebstoffen Informationen
zu erhalten
iiber
ihren PH-Wert, die
Emission
gefahrlicher fluchtiger Inhaltsstoffe,
die
Flexibilitdt/Festigkeit
dieser
Klebstoffe
und ihre
Vergilbung
nach
Alterung
unter
Belichtung
und unter LichtausschluJ3. Bewertet wurden 27
Klebstoffe auf
der Basis von
Polyvinylacetet (PVAC)
und 25
Acrylharzklebstoffe.
Die
Messungen
der PH- Werte
ergaben,
daJ3 die PVAC-
Klebstoffe
saurer waren als die
Acrylkleber.
Die
Alterung
unter LichteinfluJ3
fuhrte
zu einer
Verringerung
des
PH-Wertes bei beiden Sorten. Die
PVAC-Homopolymere zeigten generell
einen hdheren
Sduregrad
als die
PVAC-Copolymere,
wdhrend viele
Butylacrylatklebstoffe
im neutralen Bereich
lagen.
Die Analyse der
Fliichtigen
Bestandteile aller Kleber wies eine Emission verschiedener Ester und
Ldsungsmittelrackstdnde
nach. Die
PVAC-Klebstoffe
setzten nennenswerte
Mengen
von
Essigsdure frei.
Den
Untersuchungsergebnissen
zufolge diirfte
die
Bildung
von
Essigsdure
nach einer Abbindezeit von mehreren Wochen bei diesen
Klebstoffen
jedoch
zu keinen akuten Gesundheitsschdden
fiihren.
Grundsdtzlich verloren PVAC- und
Acrylklebstoffe
bei
der
Alterung
in Dunkelheit an
Flexibilitdt,
wobei die
PVAC-Klebstoffe gegeniiber
den
Acrylen
mehr
Festigkeit
und
geringere
Flexibilitdt
zeigten.
Dabei boten die
PVAC-Copolymere
wiederum mehr
flexibilitdt
und behiel-
ten diese auch besser als die
Homopolymere.
Die
PVAC-Klebstoffe vergilbten
etwa zweimal so schnell wie die
Acrylklebstoffe.
Fuir sdmtliche
Klebstoffsorten
bedeutete
Alterung
unter
Belichtung
eine raschere
Vergilbung
als die
Alterung
bei Dunkelheit. Fur das leichtere Ablesen und Zuordnen der einzelhen
Testergebnisse fur
jeden Klebstofftyp
wurden die Resultate tabellarisch
angeordnet.
Resumen-En 1983 el Canadian Conservation Institute
(CCI)
inici6 un
proyecto para
evaluar 27 adhesivos de
acetato de
polivinilo (PVA C) y
25 adhesivos acrilicos sobre la base de
pH,
emision de voldtiles
daniinos, flexi-
bilidad/resistencia
y
amarilleo
despues
de
envejecimiento bajo
condiciones claras
y
oscuras. Las mediciones de
pH
demostraron
que
los adhesivos P VAC eran mas acidos
que
los adhesivos acrilicos
y que
el
envejecimiento
por
luz solia disminuir el
pH
de ambos
tipos.
Los
homopolimeros
PVAC eran
generalmente
mas dcidos
que
los
copolimeros
PVAC
y
se encontr6
que
muchos adhesivos acrilicos
que
contienen acrilato de butilo son neu-
tros. El andlisis de
compuestos
voldtiles de adhesivos PVAC
y
acrilicos demostrd
que
emiten varios esteres
y
compuestos
residuales de disolventes,
pero
sdlo los adhesivos PVAC liberaban cantidades
apreciables
de acido
acetico. Los resultados indicaban
que despues
de un
periodo
inicial de curado de varias semanas,
la evolucion
de dcido acetico de adhesivos PVAC no debe
presentar
un
riesgo pronunciado.
Por lo
general,
tanto los adhe-
sivos PVAC como los acrilicos se volvieron menos
flexibles despues
del envejecimiento en oscuro
y
los adhe-
sivos PVAC
poseian
mas resistencia
y
menos
flexibilidad que
los acrilicos. Los
copolimeros
PVAC
evidenciaron
y
retuvieron mds
flexibilidad que
los
homopolimeros
PVAC. Los adhesivos P VAC amarilleaban
aproximadamente
dos veces mds
rdpidamente que
los adhesivos acrilicos
y
el
envejecimiento por
luz solia
causar un amarilleo mds
rdpido
en todos los adhesivos
que
el
envejecimiento
en oscuro. Se han
preparado
tablas de los resultados de cada
prueba para
cada adhesivo
para
una
perspectiva global y
la evaluacion de los
datos.
(1996)
19-44 44

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