Air Release in PVC Plastisols

J. R. DEFIFE
Diamond Shamrock Corporation
Painesville, Ohio 44077

The ability of a PVC plastisol to liberate entrapped air during mixing

and processing is an important factor to the processors. This property,
known as air release, is affected by several variables such as resin,
plastisol viscosity, surface tension, surfactant system and plasticizer
type. A study was conducted to obtain a more fundamental understand-
ing of the effects of these variables on air release. Complicating the
accurate study of a plastisol’s air release properties is the fact that
current test procedures such as the vacuum rise, syringe test and Huff
or ring test each have limitations imposed by either plastisol properties
or by testing technique. Any one of these procedures alone may not
adequately measure air release. This paper, in addition to studying the
factors affecting air release, discusses these testing limitations and
makes recommendations as to the best methods for evaluating air
release properties in the laboratory.

INTRODUCTION
uring the preparation of a PVC plastisol, large
D amounts ofair can be entrapped in the plastisol
which, if not removed, can cause poor product qual-
ity or hold ups in a processing line. The ability of a
plastisol to liberate this entrapped air is known as
air release. In most cases, air is removed by pulling
a vacuum on the plastisol either during or after it
has been mixed. Ifthe plastisol does not release the
entrained air during this deaeration step, frothing
may occur. This can slow the process and also dam-
age equipment. Also, air which is not removed dur-
ing this deaeration step will carry over into the
product and can result in poor clarity or surface
defects. I n addition to entrapment during mixing,
air can also be introduced during the processing
cycle. In a knife or coil coating operation, for exam-
ple, air can be picked up in the nip behind the knife
or roll and, if the bubble is not sheared out or bro-
ken upon spreading of the plastisol, it will result in
a defective coating. Another example is dip coating
where the plastisol which drips off of a mold will
pick up air that, if not released, can ultimately end
up in the finished product.
There are several factors which can affect the air
release properties of a plastisol. Among these are
formulation ingredients, plastisol viscosity, and
plastisol surface tension. Surface tension effects
can be related to the plastisol additives and PVC
dispersion resin. This paper discusses these factors
and their effects on air release as well as the proce-
dures which can be used to predict the air release
properties of a resin.
EXPERIMENTAL
Several testing methods were used to charac-
terize the air release properties of PVC resins. A
brief description of these procedures is listed be-
222
low:
Brookfield Viscosity-procedure for measuring
the low shear rate viscosity of a vinyl dispersion
using a Brookfield viscometer. (SPI-VD-TI)
Vacuum Rise-procedure for the determination
of a vinyl dispersion’s ability to liberate air when
under a vacuum. (SPI-VD-TBO)
Syringe Bubble-procedure for the determina-
tion of a vinyl dispersion’s ability to liberate air
which is introduced after the plastisol has been
prepared. (SPI-VD-TSO)
Huff Ring Test-procedure for the determination
of a vinyl dispersion’s air release ability.
Surface Tension-determination of the surface
tension of various liquids by means of a surface
tensiometer.
DISCUSSION
Air Release Characterization
The ability to measure the air release properties
of a PVC plastisol is of prime importance to many
processors. It is also important for a resin supplier
to have the ability to accurately predict the air re-
lease behavior of his products. Although the mea-
surement of air release is important, currently there
are only a few simple methods by which it is tested.
These include the vacuum rise procedure, syringe
bubble break test, and the Huff ring test. Despite
the availability of these standard procedures, many
processors measure air release by simply observing
the performance of a plastisol when deaerated or by
visual observation of air release in a cast film.
As typically used, tests such as the vacuum rise or
syringe bubble break cannot adequately measure
air release due to inconsistencies are due to the
complexities of the controlling mechanisms of air
release and the fact that each of these procedures
has limitations imposed by either plastisol proper-
JOURNAL OF VINYL TECHNOLOGY, DECEMBER 1980, VOL. 2, NO. 4
 Air Release in PVC Plastisols

ties, such as viscosity or by testing technique.
Complicating the thorough study of air release is
the fact that each ofthese testing methods measures
a different type of air release. The use of any one of
these procedures alone cannot adequately measure
air release. However, these tests can be used to
accurately predict air release by developing an un-
derstanding of the limitations and interrelation-
ships of each procedure, as well as knowing what
air release mechanism each method is measuring.
One of the most widely used methods for deter-
mining air release is the vacuum rise test. This test
is designed to measure the ease by which a non-
deaerated plastisol will release air when subjected
to a vacuum. It is conducted by pulling a specified
vacuum (at least 5 mm Hg) on a standard amount of
undeaerated plastisol in a graduated cylinder or
breaker. The vacuum causes the plastisol to rise to a
certain height and then breaks down as the en-
trapped air is pulled to the plastisol surface and
then liberated. The height of rise is then used as a
measure of the plastisol’s air release. The higher
the rise, the poorer the air release. The higher the
rise, the poorer the air release. This procedure can
be a valuable tool if its limitations are understood.
For example, one important limitation on the test’s
accuracy is the plastisol’s viscosity. If the plastisol
is too viscous, the vacuum is just not strong enough
to pull out the air. Subsequently, false readings can
be obtained. To illustrate this, the results of an
experiment, which utilized the addition of Cab-O-
Sil to raise the viscosity of a poor air release plas-
tisol, are shown in Table 1.I n this system, a vacuum
rise height of 3.0 cm or less is considered good air
release. As you can see, the low viscosity plastisol
with no Cab-0-Sil has a reading of more than 8.8
cm. It actually rose out of the breader used for the
test. As the viscosity was increased with increasing
levels of Cab-0-Sil can be used to enhance air re-
lease, but rather that there is a viscosity limit above
which the test results become meaningless. This
viscosity limit will vary for different amounts of
vacuum and plastisol, as well as for different types
and sizes of apparatus and, therefore, should be
established for each individual system.
Another widely used air release testing method is
the syringe bubble break test. This procedure is
Table 1. Effect of Piastisol Viscosity on Vacuum Rise Height
designed to measure the ability of a deaerated plas-
tisol to liberate air which may be entrapped during
the processing cycle, such as knife coating or dip
coating. This method does not correlate with the
vacuum rise test because they measure two differ-
ent types of air release which may be controlled by
different mechanisms. Although the syringe test
can be used as a good indicator for this type of air
release, it too has its drawbacks. The test involves
the introduction of an air bubble into a plastisol by
injecting air below the surface of that plastisol.
When the bubble rises to the surface, the time that
it takes to break is measured. This is fine except that
it is very operator-dependent. The depth below the
surface at which the bubble is injected, the in-
terpretation of the appearance of the bubble on the
surface, the amount or speed of the air injected, and
the conditioning of the plastisol are all variables
which can alter the results of the test procedure.
The best way to overcome these deficiencies is by
careful testing to establish a technique which gives
the desired reproducibility. For example, an impor-
tant factor in the syringe test is the amount of air
which is injected into the plastisol. Small variations
in this amount can result in different bubble sizes
and, subsequently, variations in the bubble break
time which is reported. Table 2 shows the effects of
increasing the amount of injected air on the bubble
break time. Care must be exercised in order to get
the best reproducibility with this procedure.
Although there are other methods for measuring
air release, the vacuum rise and syringe tests are the
most commonly used. As mentioned before, these
tests measure air release which may be controlled
by different mechanisms and, therefore, do not cor-
relate. This is shown in Table 3 . The four resins
studied although similar in molecular weight and
Table 2. Effect of Air Volume on Syringe Bubble Break Time
Formulation: 100 phr Resin
60 phr DOP
Amount of air injected Bubble break time in seconds
0.1 cc 30
0.2 cc 15
0.3 cc 12
0.4 cc 5
0.5cc 3

Formulation. Dhr
1 2 3 4 5 6

Resin A 100 100 100 100 100 100

DOP 60 60 60 60 60 60
Cab-0-Sil - 0.5 .75 1 .o 1.5 2.0
Brookfield viscosity, cps
2 hr, 2 rpm 5,600 10,600 15,000 29,000 60,000 100,000
5 rpm 5,000 8,800 13,000 19,000 41,000 80,000
20 rprn 4,700 7,000 10,000 12,000 23,000 40,000
Air release
vacuum rise
height, crn 8.8’ 8.0 5.4 3.2 2.5 1.5

JOURNAL OF VINYL TECHNOLOGY, DECEMBER 1980,VOL. 2, NO. 4 223


Table 3. Variability in Air Release
Formulation: 100 phr Resln
60 phr DOP
Resin Resin Resin
A B C D
Inherent viscosity, 1.16 1.14 1.16
ASTM D-1243-66-A
Plastisol viscosity,
cps, 2 hr Brookfield
2 rprn 7,400 7,600 7,500
5 rpm 6,500 6,800 6,700
20 rpm 5,300 6,100 5,900
Air release
Vacuum rise, cm 2.0 6.5 2.1
Syringe bubble break, s 904 8.0 6.5
viscosity, exhibit different air release characteris-
tics. I n one case, Resin A has a good vacuum rise
value, but poor bubble break time. This indicates
that this resin would deaerate easily after mixing,
but that problems may b e encountered during
processing when new air is introduced. Resin B, on
the other hand, shows a poor vacuum rise and a
good syringe time. This indicates that this resin
would be difficult to deaerate but, after the air has
been removed, it would process easily. Resin C has
the best of both worlds with good vacuum rise
height and bubble break time and should present
no problems while Resin D has poor air release
overall.
The basis regarding the above statements for
each resin's air release properties is that there are
different controlling mechanisms in each case. In
the first case, Resin A, the air which is entrapped
during mixing is located at the resin particle's sur-
face within the plastisol. This air is readily released
when pulled under vacuum. However, an air bub-
ble, which is introduced into this plastisol and rises
to the surface as in the syringe test, will not break
due to surface tension phenomena which will be
discussed later. This bubble, if not sheared out
during processing, will result in a surface defect.
On the other hand, the air which is entrained dur-
ing the mixing of Resin B is held tightly at the resin
particle's surface and is not liberated under vac-
uum. If this air is not removed, serious quality prob-
lems can occur. Resin C, which has a good vacuum
rise value and syringe bubble break time, will de-
aerate easily and any air which is entrapped during
processing will be quickly liberated. Resin D,
however, has both a poor vacuum rise height and
syringe break time and, therefore, will present
problems in deaeration and subsequent process-
ing.
In addition to understanding the limitations and
interrelationships of the above methods, slight
modifications in these tests enable the processor to
gain additional knowledge of the plastisol's air re-
lease properties. One of these modifications is the
monitoring of the time it takes for the plastisol to
224
J. R. Defje
break down in the vacuum test. In a 100/60 resin/
DOP system, a good air release material will break
within 50 s after the vacuum is started. This again is
Resin subject to the particular formulation and, thus,
should be established for each individual system.
As with the vacuum rise test, a modification can be
1.17
made with the syringe bubble break test. Part ofthe
conditioning of the plastisol for this procedure is a
deaeration step where the plastisol is subjected to a
8,000 vacuum until deaeration is completed. The time it
7,200 takes for this step is dictated by the amount of plas-
6,400 tisol used, the amount of vacuum, the plastisol's
viscosity, and, of course, its air release ability. If
8.8+ done carefully, the time it takes for complete deaer-
ation of the plastisol can be correlated to the vac-
90 + uum rise procedure. Figure 1 shows this correlation
for plastisols with a viscosity limit of 20,000 cps ( 2
hr, S rpm Brookfield). The plastisols in this system
have good air release via vacuum rise (i.e., 30 em
rise) and deaerate in less than SO mins. If this type
of correlation holds true for a particular system, it
can be used either to give additional information
regarding air release or to consolidate the vacuum
rise test with the syringe test.
In order to get the best possible understanding of
how a plastisol will perform as to its air release
properties during processing, both of these proce-
dures should be used as quality control tools,
Air Release Variables
The controlling mechanisms of air release are
very complicated. There are several factors which
can affect it. Among these are resin, plastisol viscos-
ity, plastisol surface tension, resin surfactant sys-
tem, plasticizer type, and level used in the plastisol.
Very little has been published in the literature con-
cerning air release, primarily because of the
difficulties encountered in measuring it and the
inconsistencies in air release from resin-to-resin.
However, a general understanding can be obtained
by a few simple techniques.
The effects ofplastisol viscosity on air release can
easily be studied by testing air release at various
plasticizer levels. Figures 2 and 3 show the effects
of increasing plasticizer level on air release mea-
I , J I I 1 I
,,,*,/*,,"l, T,,li, U,_j I 1 0 I. I, v '!8#1)1
Fig. 1 . Vacuum rise height tis deuerution time of u PVC plastisol.
JOURNAL OF VINYL TECHNOLOGY, DECEMBER 1980, VOL. 2, NO. 4
 Air Release in PVC Plustisols

with the Same viscosity can have drastically differ-

ent air release properties. Table 4 compares the air
release properties of four plastisols with cornpara-
b]e viscosity which were made from different res-
ins of the same molecular weight. Each of these
resins was made with a different surhctant type
which will affect air release. This will be discussed
later in this paper. The vacuum rise and syringe
bubble break test show that each ofthese resins has
distinctively different air release ability. Thus,
plastisol viscosity in itself does not determine air
/ - ’ -l - + - I release.
P L h F l i C l l i R LEV7 PI Y F / X I 0 F , ? i i S 1 N It is believed that air release properties of a plas-
Fig. 2 . Effect of increasing plasticizer level on uir releuse (vuc. tisol are also related to surface tension phenomena
rise). at the air bubble and plastisol interface. This can be
manifested at the plastisol’s surface and/or at the
resin particle’s surface within t h e plastisol.
Changes in this surface tension will alter the air
release ability of a given resin in a plastisol.
Surface tension in a plastisol is primarily affected
by surfactants or emulsifiers, additives, and plas-
ticizer type. Plasticizers with different inherent
surface tensions can affect the bubble-plastisol
interface and, subsequently, air release. This was
shown by testing the air release of three different
resins of similar molecular weight and viscosity,
but differing air release in various plasticizer sys-
I L I 1 I I
tems. The plasticizers used in this study had vari-
1 P P
ous surface tensions. They include butyl benzyl
Fag. 3. Effect of plustacazer level on uar release vzu syrange phthalate (BBP), dioctyl phthalate (DOP),
bubble breuk
diisodecyl phthalate (DIDP),and dialkyl phthalate
(Santicizer 711), dioctyl adipate (DOA), and cresyl
diphenyl phosphate (Santicizer 140). The data ob-
sured via vacuum rise and syringe bubble break. As
tained on viscosity, air release, and plasticizer sur-
plasticizer level is increased and the viscosity de-
face tension is shown in Table 5 . The surface ten-
creased, both the vacuum rise and syringe bubble
sions of the plasticizers ranged from 29 to 42
break times decrease. The plasticizer used for this
dynes/cm. Note the different air release values of
test was DOP. Although this general relationship of
the three resins in the DOP system. This indicates
plasticizer viscosity to air release exists for a single
that these resins have varying air release. However,
resin, it does not hold for different resins. Resins
as the surface tension of the plasticizers varies, the
air release also changes. A low surface tension plas-
Table 4. Effect of Resin Type on Air Release ticizer will improve air release while a high surface
tension plasticizer will improve air release. The
Formulation: 100 phr Resin effect oflowering surface tension on a material with
60 phr DOP poor air release, such as Resin C, is more evident
Resin Resin Resin Resin than in resins with good air release. It should be
A B C D
noted that although viscosity does play a role in air
Inherent viscosity, 1.16 1.15 1.17 1.16 release, it is not the dominant factor. This is shown,
ASTM D-1243-66A for example, by the D l D P system where, although
0.2 g/100 ml
cyclohexanone Resin B has the highest viscosity ofthe three resins,
@ 30°C it does not have the poorest air release. Also note
Plastisol viscosity,
that the use of BBP or phosphate plasticizers yield
cps, 2 hr Brookfield, very poor air release and are not recommended for
2 rpm 8,500 9,100 8,300 8,700 use in operations where good air release is re-
5 rpm 6,300 7,000 6,500 7,100 quired.
20 rpm 5,200 6,700 5,200 6,900 Perhaps the most dominant factor which affects
Vacuum rise height, the interfacial surface tension between an air bub-
em 1.5 3.0 5.4 8.8+ ble and a plastisol is surfactant. This surfactant or
Syringe bubble
break, s 6.0 15.5 45.5 Did not break emulsifier can either be present on the dispersion
resin as a result of its polymerization or can be
Surfactant type A B C 0 added to a plastisol during its compounding. The

JOURNAL OF V I N n TECHNOLOGY, DECEMBER 1980,VOL. 2, NO. 4 225

 Table 5. Effect of Plastlclzer Surface Tension on Air Release

Formulatlon: 100 phr Resin

60 phr Plasticizer
DOA DlDP SANTCIZER 711 DOP BBP SANTCIZER 140
Resln A B C A B C A B C A B C A B C A B C
Surface tension, ---29--- ---% --- --- 29.4 - - - - - - 33 - - - ---- 40---- - - - - 42 - - - -
dyneslcm
Rheology,2hr 1850 5400 5300 7800 10,200 9800 4640 7300 7800 7040 7200 8000 10,400 10,900 10,500 10,800 11,200 11,500
5 rprn Brookfields,
CPS
Vacuum rise. cm 1.1 2.0 3.0 1.1 2.1 3.2 1.3 2.3 4.0 2.1 2.7 6.0 5.2 4.9 8.8+ 6.6 6.8 8.8+
Syringe bubble
break, s 1.2 7.5 10.0 1.5 8.0 12.0 4.1 10.6 15.5 6.8 25.5 40.7 60+ 604 60+ 60+ 60+ 604

latter type of surfactants are generally ethers or ticular resin is significantly effected by the type and
esters of ethylene glycol, diethylene glycol, or level of surfactants incorporated onto the resin. Re-
polyethylene glycol. Table 6 shows the effective- ferring back to Table 4 , these four resins, which
ness ofone ofthese surfactants on the improvement yield similar plastisol viscosity but range in air re-
in air release; they also serve to reduce the plas- lease properties, are made with different surfactant
tisol’s viscosity. However, care should be taken systems.
when using these types ofaides, due to heat stabil-
ity degradation. Typical usage levels for these CONCLUSIONS
products range from 0.5 to 1.5 phr. Although the study of a plastisol’s air release
One of the most important controlling factors of properties is complicated due to the interrelation-
air release is the type and level of surfactant or ships of plastisol viscosity, surfactant type, and
surfactant additive which is incorporated on the formulation ingredients, a processor can
resin during its polymerization. There are a wide adequately predict the performance of a resin by
variety of these surfactant which are a necessity for combining current testing procedures, such as the
the production of paste resins. In some cases, other vacuum rise and syringe bubble break tests. How-
additives are incorporated onto the resin to en- ever, for these tests to become more discriminating
hance various plastisol properties, such as air re- tools, their limitations and interrelationships must
lease, viscosity, foam cell structure, etc. The acting be understood. This study has shown that factors,
mechanisms of these surfactants are very compli- such as a plastisol’s viscosity and testing technique,
cated. Suffice it to say that the variability in air can affect the accuracy of these procedures. An un-
release from resin-to-resin and lot-to-lot of a par- derstanding of these limitations in a particular sys-
tem, along with some modifications of the tests,
Table 6. Effect of Surfactant on Air Release enable the testor to use these methods to more
100
accurately predict air release properties of a plas-
Resin A 100 100 100 100
tisol.
DOP 60 60 60 60 60 The controlling mechanisms of air release are
Surfactant P - 0.25 0.5 1.o 1.5 quite complex. It has been shown that plastisol
Brookfield Visc
viscosity, formulation ingredients, surfactant type
2 hr, 2 rpm 14,200 12,200 10,000 8,000 6,500 and level, and plasticizer type each play an inde-
5 rpm 11,100 9,500 7,900 6,500 4,550 pendent role in determining the air release proper-
20 rpm 8,800 8,700 5,200 5,200 3,250 ties of a resin or plastisol. Perhaps the most domi-
Air Release nant factor of these is the surfactant type which is
Vac rise, cm 4.5 4.2 3.2 3.0 2.5 used during the polymerization of the dispersion
resin. It is the interactions of these mechanisms
Syringe bubble which make air release properties vary from resin-
break, s 50 45 25 15 12
to-resin and lot-to-lot.

226 JOURNAL OF VINYL TECHNOLOGY, DECEMBER 1980, VOL. 2, NO. 4