April 1953 INDUSTRIAL AND ENGINEERING CHEMISTRY
LITERATURE CITED (14) Lockwood, A. R., Chemistry and Industry, 1951, 46-7; i l l f g .
(1) Brimhall, B., IND. ENG.CHEM.,36, 72-5 (1944).
* (2) Chanda, S. K., Hirst, E. L., Jones, J. K. N., and Percival,
E. G. V., J . Chem. Soc., 1950,1289-97.
(3) Chem. Eng. News, 29,650-4 (1951).
(4) Connell, J. J., Hirst, E. L., and Percival, E. G. V., J . Chem. Soc.,
1950,3494-500.
(5) Corn, 6,4 (1950).
(6) Evans, T. H., and Hibbert. H., “Bacterial Polysaccharides.”
Scientific Report Series No. 6, New York, Sugar Research
Foundation, April 1947.
(7) Graefe, G..Die Stdrke, 3,3-9 (1951).
. (8) Hehre, E.J., private communication.
(9) Jeanes, A., and Wilham. C. A., J. Am. Chem. SOC.,72, 2655-
7 (1950).
(IO) Jeanes, A., Wilham, C. A., and Miers, J. C., J . Bid. Chem., 176,
603-15 (1948).
(11) Katz, J. R., and Weidinger, A., 2. physik. Chem., A184, 100-
22 (1939).
(12) Kerr, R. W.,ed., “Chemistry and Industry of Starch,” 2nd ed.,
pp. 174,345-55, New York, Academic Press, 1950.
(13) Lansky, S.,Kooi, M., and Schoch, T. J., J. Am. Chem. SOC.,71,
4066-75 (1949).
Improved Portland Cement Mortars
with Polyvinyl Acetate Emulsions
JACOB M. GEISTI, SERVO V. AMAGNA2, AND BRIAN B. MELLOR
Department of Chemical Engineering,
Massachusetts Institute of Technology, Cambridge 39, Mass.
.P ORTLAND cementmortarsandconcretesareusedasbuilding
materials because among other properties they have high
compressive strengths, good bonding strengths, and resistance to
weathering. Their principal weakness lies in a normally low
tensile strength, a quality which has been corrected by various
means.
Most improvements of the properties of concretes and mortars
have been made without admixtures, by controlling the mix pro-
portion of the ingredients-the water to cement ratio being the
most important factor ( 6 , 7 , 8, 13, 17, 19). Additives such as
rubber latex have been incorporated whh portland cement t o
produce floorings which are claimed t o have high resiliency (11,
I d , 16, 20-25). Other additives such as resins, metallic oxides
and salts, sugar, powdered metals and nonmetals, organic fibers,
and gelatin have been used in an attempt to improve one or more
properties of concrete mixes ( 5 , 1 5 ) .
Polyvinyl acetate (PVA) emulsions are now commonly used in
numerous industrial applications. Recently, polyvinyl acetate
mixtures with portland cement were reported for surfacing con-
crete floors, for making joints between concrete blocks, and for
. mending broken cement surfaces (2, 9,10, 11), b u t apparently no
. . work had been done to determine the exact nature of the new
combination. The work described in this paper was initiated t o
study the effects of using polyvinyl acetate emulsions as admix-
tures with portland cement mortars and concretes.
GENERAL PROCEDURE
TESTSA N D COMPOSITIONS.Throughout the tests, A.S.T.M.
(3) standard procedures were used wherever applicable. The
procedures were modified when necessary, as dictated by the
nature of the mortars and the tests.
Tensile and compressive mortar specimens were prepared fol-
1 Present address, Hebrew Institute of Technology, Haifa, Israel.
2 Present address, California-Texas Oil Co., Ltd., New York, N. Y.
759
Chemist. 23. 49-55 (1952). Reoort of talk.
(15) McCready, R. M.,Guggolz, J., Siiviera, V., and Owens, H. S.,
Anal. Chem., 22,1156-8 (1950).
(16) Meyer, K.H., Noelting, G., and Bernfeld, P., Helv. Chim. Acta,
31,103-5 (1948).
(17) Montgomery, E. M., Weakley, F. B., and Hilbert, G. E.,J . Am.
Chem. Soc., 71,1682-7 (1949).
(18) Northern Regional Laboratory, unpublished results.
(19) Ricketts, C. R.,Lorenz, L., and Maycock, W. d’A., Nature, 165,
770 (1950).
(20) Senti, F. R., and Hellman, N. N., Abstracts of Papers, 121st
Meeting, AM. CHEM.SOC., Milwaukee, Wis., March 30 to
April 3,1952.
(21) Stacey, M., and Pautard, F. G., Chemistry & Industru, 1952,
1058-9.
(22)Thorsen, G.,and Hint, H., Acta Chir. Scand., Suppl. 154 (1950).
(23)Whiteside-Carlson, V.,and Carlson, W. W., Science, 115, 43
(1952).
RECEIVED for review September 8, 1952. ACCEPTED December 15, 1952.
Presented before the Division of Sugar Chemistry at the 122nd Meeting of
the AMERICAN CHEMICAL SOCIETY, Atlantic City, N. J.
lowing A.S.T.M. specifications and with ratios of sand to cement
of 3 t o 1 for tensile briquets and 2.75 to 1 for compressive cubes
and varying:
1. T h e ratio of polyvinyl acetate to cement from 0 t o 0.56
2. The ratio of dibutyl phthalate plasticizer t o polyvinyl
acetate from 0 t o 0.2
3. T h e ratio of water t o cement for some tensile specimens
from 0.32 t o 0.56
4. The particle size of the polyvinyl acetate
(These ratios are weight ratios-e.g., 0.2 PVA t o cement would
be 1 part by weight PVA to 5 parts by weight cement.)
Selected compositions were further tested for impact strength,
abrasion resistance, bond strengths of mortar t o steel and mortar
t o concrete, corrosion resistance, air entrainment, water adsorp-
tion, and coefficient of expansion. Tensile and compressive
specimens were also examined microscopically.
CURINQCONDITIONS.The test specimens were cured a t dif-
ferent conditions and for different lengths of time. A.S.T.M.
test methods for tensile and compressive tests (5)specify t h a t
curing of mortar test specimens shall be under water after re-
moval from the molds. Curing in a fog room a t 70 o F. with 100%
relative humidity was originally selected for this work, since this
represents the best possible curing condition, for plain cement
mortars, which can be obtained in the field. It was observed, as
was expected, t h a t the 28-day tensile strengths of plain mortars
cured in the fog room were less (by 30%) than the tensile strengths
of plain mortars under water.
I n marked contrast t o the normal behavior of plain mortars,
the 28-day tensile strengths of mortars containing polyvinyl ace-
tate were equal or greater when cured in the fog room, than when
cured under water. T o investigate this behavior further, speci-
mens were cured in a room a t 70” F. with 50% relative humidity.
Under these new curing conditions, although plain cement mor-
tars were weaker, the mortars containing polyvinyl acetate were
stronger. A few additional tests were made in which specimens
760 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 45, No. 4

24 0
KEY DAYS HUMIDITY
0 28 100%
C U R I N G AT 7 0 ° F
KEY DAYS HUMIDITY
0
I-
s 160
z
0
l-
a 120
(3
z
'w3 80

40

0.2 0.3 0.4 0.5

n
v-

POLYVINYL ACETATE TO CEMENT RATIO 0 0.1 0.2 0.3 0.4 0.5

Figure 1. Relative Tensile Strengths of Cement POLYVINYL ACETATE TO CEMENT RATIO
AIortars
1.0 = 290 lb./sq. inch
Figure 2. Tensile Elongations at Rupture
1.0 = 9 X 10-5 inch/incli

(Polyco 471). Maximum improvement in physical propei ties

wap obtained a t a polymer to cement M eight ratio of 0.2 without
plasticizer, by curing in a room a t an average relative humidity
of 35%. At 28 days, tensile strengths were ten times that of
normal cement mortars cured under similar conditioiis and three
times that of normal cement mortars cured under water.
Some properties of mortars containing polyvinyl acetate emul-
sion (Polvco 470) and cured a t various conditions have been com-
pared with the properties of plain cement mortaIs cured in a fog
room a t 100% relative humidity and 70" F. in Figures 1 to 6.
The fog room curing represents the best possible curing condi-
tions, for plain cement mortars, which can be obtained in the
field. Each point represents the average of at least three speci-
mens and in most cases of six specimens made from the same batch
of mortar.
Some tests, such as abrasion resistance, corrosion resistance,
and impact resistance were made only with specimens which
were cured in a fog room a t 100% relative humidity. It is prob-
able t h a t for the m6rtars containing polpin: I acetate these
0 0.1 0.2 0.3 0.4 0,5 properties mould have been improved even mole if cuiing h:rd
POLYVINYL ACETATE TO C E M E N T RATIO been carried out in a dry atmosphere.
Figure 3. Relative Tensile Moduli of Elasticity For mortar specimens containing a polyvinyl acetate to cenirnt
1.0 = 7,050,000 Ib./sq. inch ratio of 0.2, the following observatione have been recorded ftoni
the detailed data published in several theses (1, 4, 14, 18).

were cured in a room with varying temperatures and humidities,
and others were cured outdoors during the months of December
and January where they were subjected t o extreme freezing and
thawing conditions.
MATERIALS.The polyvinyl acetate emulsions used were
American Polymer Corp. Polyco 469, 470, and 471. The cement
%as Type I1 manufactured by the Catslcill Plant of the North
American Cement Corp. The Ottawa sands were obtained from
t h e Ottawa Silica Co. and the dibutyl phthalate plasticizer was
identified merely as technical grade.
RESULTS
A polyvinyl acetate emulsion with a nonionic emulsifier and
with particle diameters from 1 t o 5 microns (Polyco 470) was
found t o be more effective as an admixture than a similar emul-
sion with particle diameters from 2 to 10 microns (Polyco 469) or
an anionic emulsion with particle diameters from 0.5 to 2 microns
1. The tensile strengths of mortars cured in a dry atmosphere
were three to four times that of plain cement mortars cured in afog
room and eight to ten times that of plain cement moItars cuied
in a drv atmosphere (Figure 1).
2. The elongations a t rupture for tensile specimens cured in a
dry atmosphere were about twenty times the elongation a t rupture
of plain cement mortars, cured either in a dry atmosphere or in
the fog room (Figure 2 ) .
3. The compressive strengths of mortars cured in a room a t
50% relative humidity M-ere only 70% of the strength of plain
cement mortar cured in a fog room but more than three times
that of Dlain cement mortar cured in a room a t 50% . - relative
humidity (Figure 4).
4. For specimens cured in a dry atmosphere, the strength of
the bond to steel was one and a half times and the strength of
the bond to concrete surfaces was ten times that of plain cement
mortars cured in a dry atmosphere.
5 . Since 50% relative humidity a t 70" F. approximates usual
indoor drying conditions, the mortar can he left t o set and
harden by itself, without the wetting required for plain cement
mortars t o obtain high strengths. This was confirmed by the
strength of the tensile specimens cured in a room with relative
 April 1953 INDUSTRIAL AND ENGINEERING CHEMISTRY 761

12 I
I CURING AT 70°F
Ia
- C U R I N G AT 7 0 ° F K E Y DAY H U M I D I T Y
a K E Y DAYS HUMIDITY
100 Ye I
(3
5 0 Ye -I-0
z
w a
a a
ti 0.8 z
2
W
2 c
U
v) z
0.4 K
a 0
LL
a. w
5 a
0
0 0
0 0.I 0.2 0.3 0.4 0.5
POLYVINYL ACETATE TO CEMENT RATIO
Figure 4. Relative Compressive Strengths 0 0.1 0.3
0.2 0.4 0,5
1.0 = 5220 lb./sq. inoh POLYVINYL ACETATE
TO CEMENT RATIO
humidities varying from 25 t o 45% and with temperatures vary- Figure 5. Relative Compressive
ing from 65" to 85" F. Qeformations a t Rupture
6. The mortar containing a polyvinyl acetate to cement ratio 1.0 = 0.0056 inch/inch
of 0.2 was more workable and flowed more easily than did plain
cement mortars with the same water to cement ratio. It did not
require the extra tamping and ramming essential t o compact
the plain mortars. The water to cement ratios in most of the
tests were dictated by A.S.T.M. consistency standards t o be 0.6
for compressive cubes and 0.43 for tensile briquets. Figure 7
shows t h a t decreasing the water content within the limits of work-
ability increased the tensile strength of mortars containing
polymer. This was not possible with the plain cement mortar
which was a t the lower limit of workability and was a "dry-mix."
7. The modulus of rupture for the mortar cured in the room
at 50% relative humidity was forty times t h a t of plain mortars
cured in the fog room. The impact strength of mortars cured in
the fog room was 20% more than the impact strength of plain
mortars cured in the fog room. Thus the new material is tougher
and can absorb more energy from impacting bodies before break-
ing or cracking.
8. Mortars cured in a fog room when compared with plain
cement mortars cured in a fog room had about ten times the
resistance t o abrasion, at least the same resistance to freezing and
thawing, and the same or greater resistance t o corrosion by alkali,
organic solvents, and dilute inorganic acids. They were more
resistant t o concentrated hydrochloric acid, but less resistant to
boiling water.

I n considering the properties of plain cement mortars when

POLYViNYL -ACETATE TO CEMENT RATIO
cured in a fog room, i t should be realized that these curing condi-
tions are better than those obtained in the field and t h a t the Figure 6. Relative Compression iModuli of
actual field strengths of the usual plain portland cement mortars Elasticity
are considerably less. 1.0 = 1,750,000 Ib./sq. inch

MICROSCOPIC STUDY
EXAMINATIOX LIGHT. The
BY TRANSMITTED
OF EMULSIONS
b particle sizes of the emulsions as estimated by a microscale (Figure
8) tallied very closely with the particle size determinations made
by the American Polymer Corp. with the aid of an ultramicro-
scope. These were Polyco 471, 0.5 t o 2 microns; Polyco 470,
1 to 5 microns; and Polyco 469, 2 to 10 microns. The particles
were spherical in shape and appeared t o be well dispersed.
In dilute emulsions with plasticizer, a distinct layer of plasti-
cizer was evident around the particles. This fact was verified b y
a microscopic view of the dispersion, using a red oil-soluble Calco
dye, which imparted color only to the layer of dibutyl phthalate.
The photographs were taken after the smears on the slides were
diluted to eliminate, as much as possible, all b u t one layer of the
particles.
EXAMINATION OF GROUNDMORTARSURFACES BY METALLO-
GRAPHIC MICROSCOPE AND CAMERA. Figure 9 represents mortars
with polyvinyl acetate t o cement ratios from 0 to 0.5. No plasti-
cizer was used in these mixes. Specimens were cured at 100%
humidity and 70' F. for 28 days and dried under room conditions
for a n additional 28 days.
I n the plain cement mortar (Figure 9, A ) the large surfaces are
sand grains, The masses between them are the products of
cement hydration which form a gel structure. T h e voids in the
gel are fairly well defined. I n the mortar with a 0.2 polyvinyl
acetate t o cement ratio (Figure 9, B ) the shaded areas are poly-
vinyl acetate and the voids have been filled with polymer. T h e
preponderant continuous phase is still cement gel. The bond
between the sand grains and the cement mass is mainly between
the hydrated cement and the silica surface, with some direct con-
tact between the polyvinyl acetate and the sand where voids have
been filled up by polymer.
I n the mortar with a 0.3 polyvinyl acetate to cement ratio
(Figure 9, C) there is apparently more polymer within the
762 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 45, No. 4

cement matrix in direct contact with the sand grains. The was a result of the rapid escape of water from the mixture. The
mortar with a 0.4 polyvinyl acetate to cement ratio (Figure 9, D ) briquet containing 0.2 polvyinyl acetate to cement ratio (Figure
shows a continuous phase of more than three-quarters polyvinyl 12, B ) had tensile strengths ranging over 1000 pounds per square
acetate. I n the photograph which illustrates a mortar with a inch. The photograph shows a well compacted mass of hydra-
polyvinyl acetate t o cement ratio of 0.5 (Figure 9, E ) the cement tion products and polyvinyl acetate, with the cement gel forming
hydration products can be seen dispersed in the continuous poly- the bulk of the mass. A few bubbles are present.
mer phase. The mortar containing 0.2 polyvinyl acetate to cement ratio
and 0.1 dibutyl phthalate t o polyvinyl acetate (Figure 12, C) is
2, less compact, apparently due to the presence of plasticizer. AI-
though this mixture had less strength than t h a t with no plasti-
cizer, its tensile strengh was still twice that of plain cement mor-
tar cured under the best conditions,
C U R I N G AT 7 O o F
KEY PVA TO CEMENT DISCUSSIOY
I,
Workability. BEHAVIOR DURING MIXING. Workability is an
0 -3 intangible property describing the ease with which the mortar or
concrete can be handled. Plain cement mortars usually exhibit
maximum strength a t the lowest water to cement ratio consistent
1. with the minimum workability. This is usually the water t o
cement ratio determined by A.S.T.M. consistency tests (Figure 7 )
and is several times the amount of water required to hydrate the
cement fully (19).
I CEMENT RATIO 0.43 1 I Descriptions of the workability of mortars with a constant
v,
E 1,o
water to cement ratio of 0.43 and with various polyvinyl acetate
to cement ratios are given in Table I. The most workable mortar
I- had a polymer to cement ratio of 0.2. Subsequent measurements
of physical properties showed that this polymer to cement ratio
produced mortars with optimum properties. This implies that
workability may be a very important factor in determining the
O. 6
final properties of mortars.
Oa32 0.40 0.48 0.56
W A T E R TO CEMENT R A T I O
Figure 7 . Effect of Water to Cement Ratio on
Seven-Day Tensile Strengths
1.0 = 270 lb./sq. inch
TABLE
I, WORKABILITY
OF MORTARS
Tensile specimens, water t o cement ratio
Polyvinyl acetate emulsion, Polyoo 470
- 0,43
Particle diameters 1-5 microns, nonionic emulsifier
Polymer t o Cement Workability of Freshly
Mixture No. Ratio Mixed Mortar
EXAMINATION O F FRACTURED SURFACES B Y ULTROPAK hfICRO-
0 Workable h u t nonflowing
SCOPE. Figure 10 shows, a t a magnification of 65 diameters, the 0.1 Workable, soft butterlike
consistency
surfacesof briquetscured for 28 days a t 100% humidity and 70 O F . , 0.2 Very workable, thin, and
and then dried under room conditions for another 28 days. easy flowing
0.3 Workable. soft butterlike
With polyvinyl acetate t o cement ratios of 0.1 and 0.2 (Figure 10, consistency
0 4 Stiff, h u t more workable
B , C) the polymer phase was discontinuous. At a ratio of 0.3 t h a n No. 6
the polymer phase showed some continuity (Figure 10, D ) and 0.56 Very stiff, just workable
the hydrated cement was almost totally dispersed in the polymer
phase a t higher polymer to cement ratios. The presence of poly-
vinyl acetate is generally indicated by a graying or darkening of The polyvinyl acetate emulsion, when diluted with sufficient
the normally light colored cement gel structure. With plasti- water, probably acted as a dispersing agent for the cement parti-
cizer, Figure 11, the same phase change was noted. The plastici- cles and for the sand. Increasing the polyvinyl acetate to cement
zer seemed t o introduce more voids, and the presence of plasti- ratio to more than 0.2, while maintaining the water to cement
cizer also caused internal cracking when the specimens were dried. ratio the same as in preceding mixes, produced more tacky
Figure 12 shows the surface of briquets cured for 28 days at mortars. I n these cases, there was not sufficient water in the
50% humidity and 70” F. The first photomicrograph (Figure mix to dilute the emulsion and the resulting mortar became too
12, A ) shows plain cement mortar which is largely unhydrated, sticky.
with most particles unchanged from the original clinker. This Strength after Curing. DRY ATMOSPHERES. In the case of

Figure 8. Polyvinyl Acetate Emulsions

 April 1953 INDUSTRIAL AND ENGINEERING CHEMISTRY
B. 0.20 PVA to Cement Ratio
Figure 9. Photographs of Ground
Cube.Surfaces
BY reflected polarized light (250x1
D. 0.40 PVA to Cement Ratio
'
plain cement mortars cured a t 50% humidity, the water evapo-
'
rated before the cement could fully hydrate (Figure 12) and the
resulting mix was porous and weak in both tension and com-
pression. A microscopic examination of the cement which was
used revealed particle sizes ranging from as small as '/z micron
upwards. When sufficient polyvinyl acetate was added t o the
mortars, it filled the voids between cement particles and formed
a continuous phase around some individual or groups of cement
particles. A 0.2 polyvinyl acetate t o cement mix provided
enough polymer so that, upon hydration of the cement particles,
the voids usually left within the cement gel structures were filled
with polymer. The polymer did not, however, fill the air spaces
which result from air entrainment.
The polymer in the mix, b y virtue of the attraction of the water
on the surface of its hydrophilic particles, prevented the water
from evaporating too rapidly, and allowed the cement to hydrate
fully (Figure 12, B ) . I n the 0.2 polyvinyl acetate to cement mix,
the main strength was probably due to the cement gel structure,
reinforced by the polyvinyl acetate in the voids which also con-
tributed to the adhesion with the cement particles. As a result,
tensile strengths three t o four times t h a t of plain cement mortar
cured a t lOOyohumidity and eight t o ten times t h a t of plain mor-
t a r cured under dry conditions were obtained.
. For polyvinyl acetate to cement ratios less than 0.2, the voids
. became less filled with polyvinyl acetate, and the resulting mix-
tures were weaker than the 0.2 mix, although stronger than plain
cement mortars.
For polyvinyl acetate to cement ratios greater than 0.2, the
continuous polymer phase became predominant, and the poly-
vinyl acetate matrix was probably weaker than the continuous gel
structure.
With dry curing conditions, the compressive strength of mor-
tars with a polyvinyl acetate t o cement ratio of 0.2 was more than
763
C. 0.30 PYA to Cement Ratio
E. 0.50 PVA to Cement Ratio
three times greater than plain mortar cured at the same condition,
because the polyvinyl acetate kept the water from evaporating too
rapidly.
100% HUMIDITY AND PARTIAL DRYING.Mortar specimens
fresh from the moist curing room contained the same general
phase distributions as described for curing under 50% humidity
conditions. The polyvinyl acetate, however, not having been
allowed to dry, remained in a weaker form. The resulting ten-
sile and compressive strengths of all polymer-containing mortars
were lower than for plain cement mortars cured in the moist room.
When the specimens cured in the moist room were partially
dried in the 50% humidity room, the structure of the rigid cement
gel matrix, where continuous, remained unchanged. The polyvinyl
acetate phase shrank, due t o the loss of water. For mixtures
containing polyvinyl acetate t o cement ratios of 0.2 and lower, in
which the cement gel phase was continuous, the partial drying of
the polymer added strength by contributing some adhesive power
in the cement gel pores. This increased the strength so t h a t the
briquets with a polyvinyl acetate to cement ratio of 0.2 were
twice as strong as fully hydrated plain cement mortar, cured
under water, although only one half as strong as the same mix
cured a t 60% humidity.
For polyvinyl acetate to cement ratios of 0.3 and greater, the
continuous polyvinyl acetate phase shrank when dried. Al-
though the drying hardened the polyvinyl aeetate, the cracking
which occurred and the internal formation of voids counter-
acted this strengthening effect. The result was a mixture as
weak as when the mortar was still moist.
UNDERWATER, Underwater curing allows the fullest possible
hydration of the portland cement. It was found that as poly-
vinyl acetate was added, the resulting mortars cured under water
were weaker. Up t o the 0.2 polymer t o cement ratio, it is felt
t h a t the cement gel phase was predominant and accounted for
764 INDUSTRIAL AND ENGINEERING CHEMISTRY
A. Plain Cement Mortar B. 0.10 PVA t o Cement Ratio
Figure 10. Fracture Surfaces after Curing for 28 Days at 100% Humidity and 70' F.
No plastioizer
(Taken by Ultropak, 10 X 6.5)
the main strengths of the mortars With increasing polymer con-
tent, the polymer phase began to predominate, and curing under
water had practically the same effect as curing in the fog atmos-
phere.
Deformation Properties. Plasticizer lowered the strength both
in tension and compression, probably due t o a decrease of attrac-
tive forces between polymer particles and between the polyrnei
and aggregates. In both tension and compression, unit deforma-
tion was increased and the modulus of elasticity was decreased
with an increase in polyvinyl acetate and plasticizer.
The modulus of resilience and the modulus of rupture are ex-
pressed as the work required to deform a unit volume of material
t o the elastic limit and to the rupture point, respectively. Thrse
quantities are determined by the stress and the deformation a t
the elastic limit and a t rupture. The plasticizei contents affected
these moduli, but the polyvinyl acetate content was the control-
ling factor. An increase in polymer content resulted in an in-
crease in both the modulus of rupture and of resilience.
Abrasion Resistance. The polyvinyl acetate acted as a binder
for the cement hydration pioducts and prevented them from being
torn away by abrasive forces. The resistance to abrasion in-
creased with increasing polyvinyl acetate content, and the amount
of plasticizer did not affect this property to any significant
degree. The loss of weight of a/{-inch cubes, after abrasion for 5
minutes with a D u Pont abrasion machine was 1 6 grams for a
plain cement mortar and 0.2 gram for a mortar with a polyvinyl
acetate to cement ratio of 0.2. The specimens were cured in a
1 0 0 ~humidity
o room. I t is believed that the abrasive resistance
would be improved by dry curing a t usual atmospheric conditione,
since the resulting polyvinyl acetate structure is stronger and
tougher.
Shrinkage and Thermal Properties. Mixes containing poly-
vinyl acetate showed greater shrinkage than did plain cement
mortars, the amount of shrinkage and the rate of shrinkage vary-
ing with curing conditions. Shrinkage during 28-day curing a t
Vol. 45, No. 4
C. 0.20 PVA t o Cement Ratio
F. 0.3 PYA to Cement Ratio
507, humidity was 0.06yofor plain cement niorttLrs and 0.5%
for mortars containing 0.2 polyvinyl acetate. The main part of
the shrinkage occurred within the first few dam. However, when
mortars containing 0.2 P V A to cement were placed between
two rough concrete surfaces, the mortar mix remained unaffected
by any shrinkage, and no cracking was evident.
This apparent contradictory behavior can possibly be explained
as follows. The mortar formed an adhesive bond between the
old surfaces and when shrinkage set in to contract the mix, the
adhesion a t the boundary was sufficiently strong t o prevent rup-
ture. As a result, the central mix contracted while the material
a t the boundary between the concrete surfaces and the mortar
was elongated. Because of the high extensibility of the mixture
containing polyvinyl acetate, the material !\as able to withstand
this strain without rupturing. This important property, which
helps to prevent cracking under usual conditions, makes polymer-
containing mortars ideal for repairing cracks and for masonry
mortars, and these mortars have been used successfully i n Eng-
land, as reported by Farmer ( 9 ) .
Within the accuracy of the experiments, the coefficients of
thermal expansion of mortars with a 0.2 polyvinyl acetate t o
cement ratio, with or without plasticizer, were practically the
same as for pure cement mortar, a t about il X 10-6 inches per
inch per C.
Bond Strengths. When cured a t an average relative humidity
of 35%, the bond strength of mortars with a polyvinyl acetate
t o cement ratio of 0.2 to old mortar surfaces was 740 pounds for
4 square inches, about ten times the value of 75 pounds for plain
cement mortars. The bond strength between mortars and old
cement surfaces when cured in the fog room was practically the
same a t 160 pounds for all mixes, including plain cement mortars.
The bond strength t o steel was 1340 pounds for a 2-inch length on
a 3/8-inch bar, about one and a half times the value of 840 pounds
for plain mortars.
 April 1953 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY 765

B. 0.20 PVA to Cement Ratio C. 0.30 P V 4 t o Cement Ratio

D. 0.40 P V 4 to Cement Ratio E. 0.50 PVA t o Cement Ratio Microscale, Millimeters, 10 X 6.5

Figure 11. Fracture Surfaces after Curing 28 Days a t 100% Humidity and 70" F.
0.20 Plasticizer to PVA ratio
(Taken by Ultropak, 10 X 6.5)

'
The use of plasticizer, however, caused loss of adhesive power,
- thus reducing the bond strengths of the polyvinyl acetate mix-
tures.
Corrosion Resistance. The water absorption test with 0.2
polyvinyl acetate gave results showing that there was no signifi-
cant variation in the water absorption as compared with plain
cement mortar.
Water a t or below 70" F. did not affect the strength or physical
structures of polymer-containing briquets cured in a moist room
even after considerable immersion. At 212' F., on the other
hand, the briquets containing polyvinyl acetate spalled and d i s
integrated after boiling for about 6 hours because the thermo-
plastic polyvinyl acetate softened a t this higher temperature.
After 28-day curing in the fog room, four tensile briquets were
immersed in a corrosive medium for 4 days, then removed and
allowed to air dry for 2 days, and then tested for tensile strength.
The strength and physical structure of mortars with polyvinyl
acetate were not affected by benzene, dibutyl phthalate, brine, or
concentrated or dilute sodium hydroxide.
*
Dilute hydrochloric acid corroded both plain and polymer-
. containing cement mortars. Mortars containing polyvinyl ace-
tate were more resistant to hydrochloric acid, both dilute and
concentrated (Figure 13) than plain cement mortar, the reduction
in strength being caused primarily by reduction of cross-section
.
I
much longer periods of time-6 months to a year-with resultant
weakening. I n this case, the effect was probably due to a chemi-
cal reaction occurring within the cement mix, wherein the unhy-
drated cement particles and the oxides of calcium formed stronger
sulfate particles, which reinforced the already existing hydrated
gel structure. From these data i t is concluded that the polyvinyl
acetate cement mortar is no less resistant to sulfuric acid than is
plain cement mortar.
Air Entrainment. The mechanical method of combving
cement, aggregate, and polyvinyl acetate emulsions determines
t o a large degree the air entrainment. Mortars reported in this
paper were mixed carefully by hand in order to minimize and
standardize the amount of air entrainment due to the mixing
alone.
Only a few measurements of air entrainment were made, and
these could not be correlated simply, with either polymer contmk
or polymer particle size. However, in all cases, mortars contain-
ing polymer had entrained air contents a t least 3% above that of
plain cement mortars.
Behavior during Curing and Drying. The delay in the initial
setting time when the polymer emulsion was added to the mortar
was significant only with polyvinyl acetate to cement ratios of
0.3 or greater, since a t these compositions the continuous phase
was the polymer. For these polymer concentrations, the rigidity

area due to corrosion on the surface.
The corrosive action of d h t e sulfuric acid on the surface of the
briquets was considerably less than that of dilute hydrochloric
acid and the tensile strengths were apparently not affected.
With concentrated sulfuric acid the polyvinyl acetate appeared
t o have been carbonized on the surface. The strengths, however,
of both pure cement mortar and polymer-containing mortar were
increased by the action of concentrated sulfuric acid. This in-
crease in strength is contrary to the results of usual sulfuric acid
corrosion tests wherein specimens are immersed in the acid for
of the whole specimen depended mainly on the hardening of
polymer. With polymer contents less than 0.3 where the cement
phase was continuous, the initial set was due to the formation of
the cement gel.
For the polymer-containing mortar cured in air with a relative
humidity of 50%, the development of the final strength required
the same time as plain cement mortar. For polymer-containing
mortars cured in air a t 100% humidity, in which the polyvinyl
acetate phase did not completely dry, the initial and final setting
time of the portland cement portion of the mixes was not affected.
766 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 45, No. 4

C. 0.20 PYA t o Cement Ratio; 0.10 Plasticizcr

t o PVA Ratio
Figure 12. Fracture Surfaces after Curing 28 Days at 50% Humidity and 70" F.
(Taken by Ultropalr, 10 X 6.5)

Figure 13. Corrosion Effects of Acid Immersion for 96 Hours at 70" F.

a. Pure cement mortars
b. 0.20 PVA t o cement ratio; no plasticizer
C. 0.20 PVA t o cement ratio; 0.10 plasticizer t o PVA ratio

However, the polymer-containing mortars remained soft until
the polyvinyl acetate phase had attained sufficient rigidity.
Particle Size of Polyvinyl Acetate Emulsions. The emulsion
with particle sizes from 0.5 t o 2 microns produced mortars rela-
tively weaker than mortars prepared with emulsions with 1-
t o &micron particles. This may have been due to the fact t h a t
with the smaller particle sizes there was a greater proportion of
continuous polyvinyl acetate phase which weakened these mortar
specimens.
T i t h emulsion particle sizes of 2 to 10 microns, there was a
tendency to produce mortars slightly weaker than with particles
of 1 t o 5 microns. This behavior may have been due to the fact
that the large particles were too large t o fill the usualavoids left
within the cement gel structure and the large sizes disrupted the
normal gel arrangement of hydrated cement.
Within the limits of this investigation and for the cement used,
it is concluded that a polymer with a particle size of from 1 t o 5
microns imparts the best qualities desired in the mortar and con-
crete mixes. The emulsifier in the polymer may contribute t o
the strength of the mixes.
Resistance to Cracking. STEADY LOAD. When a steady load
is applied t o any concrete structure, the first failure almost in-
variably occurs as soon as a part of the structure is subjected to a
tensile stress exceeding its ultimate strength. With a tensile
strength above that of a plain cement mix, it is expected t h a t the
polyvinvl acetate-cement mortar with a polyvinyl acetate t o
cement ratio of 0.2 would be more resistant to cracking caused by
a steadv load. *
IVPACT STRESSES.The mortar mix with 0.2 polyvinyl acetate
t o cement ratio had greater impact strength, 2.1 inch-pounds as
compared with 1.7 inch-pounds, using h o d test specimens. An-
other criterion to support this point is the higher value of the
modulus of rupture. This means that the mortar can absorb
more energy from impinging bodies before cracking, as compared
with plain cement mortars.
THERVAL STRESSES. Temperature gradients cause uneven
 April 1953 INDUSTRIAL AND ENGINEERING CHEMISTRY
contraction or expansion of concrete, which in turn create internal
. stresses both tensile and compressive. Because of its superior
tensile strength and only slightly reduced compressive strength,
mortar containing polyvinyl acetate would probably be better
able t o withstand stresses due to sudden temperature changes
. than would plain cement mortar.
. The thermal coefficients of linear expansion of plain cement
mortars and of polyvinyl acetate cement mortars were practically
t h e same. Because of the higher values of the modulus of
elasticity for plain cement mortars, the stress caused by a linear
*
change resulting from the same temperature change would be
much greater than for the polymer-containing mortars. This
fact, coupled with the higher tensile strength of the polyvinyl
acetate mortars would seem to indicate that this new material
should be more resistant to cracking.
SIGNIFICANCE AND APPLICATIONS
One of the outstanding results of this work is that the portland
cement mortars containing polyvinyl acetate emulsions as
admixtures show maximum improvement in properties when
cured in air a t ordinary temperatures and humidities. This is in
contrast t o plain cement mortars which require a water or damp
curing in order to achieve optimum properties. This self-curing,
combined with improvements in tensile and bond strengths, ex-
tensibility, and resistance t o abrasion, impact, and corrosion,
makes this material extremely interesting as a possible means of
improving some of the qualities of portland cement mortars.
Among the uses for which this material may offer particular
advantages are:
1. Floor toppings and road surfacings for which greater
. tensile and impact strengths, greater resistance t o abrasion and
corrosion, and increased resiliency offer a considerable resistance
t o cracking
2. Wall and ceiling cement plasters where increased bond
strengths and increased resiliency, combined with self-curing
properties, make it particularly valuable
3. Masonry surfaces where self-curing and bond strengths are
. extremely important
4. Limited structural uses, such as for tanks and pipes, where
tensile strength is an important factor
It is particularly significant that the polyvinyl acetate to
cement ratio of 0.2 which produces the optimum physical proper-
ties is the most workable mixture. It is highly probable that
because of the excellent workability the physical properties can
be even further improved by decreasing the water to cement
ratio. This conclusion was supported by limited experimental
evidence.
FURTHER WORK
This work is being continued in order t o determine the useful-
ness of other polymer emulsions, and stmudiesare also under way
on the effect of the water t o cement ratio and the workability
767
of the mix and with concrete beams. The addition of pigments
and various aggregates is also under investigation. Patent
applications are being filed.
ACKNOWLEDGMENT
The authors wish t o thank Sidney J. Baum of the American
Polymer Corp. for suggesting this problem and for his opinions
during the course of this investigation. They also wish to ex-
press their appreciation t o W. Tereshkevitch and B. R. Ashton
for their assistance during the preliminary stages of this work and
to E. A. Hauser for his assistance in taking the microphotographs.
The American Polymer Corp. of Peabody, Mass., graciously con-
tributed all the materials used. J. A. Murray and A. J. O’Neill
of the Building-Engineering and Construction Department of
the Massachusetts Institute of Technology contributed useful
advice during the tests and deserve special thanks,
LITERATURE CITED
I
(1) Amagna, S. V., S. M. thesis in chemical engineering, Massa-
chusetts Institute of Technology, 1951.
(2) American Polymer Corp., Peabody, Mass., Tech. Data Sheet
P-20.
(3) Am. Soc. Testing Materials, Standards, Pt. 111 (1949).
(4) Ashton, B. R., S. M. thesis in chemical engineering, Massachu-
setts Institute of Technology (1951).
( 5 ) Barbee, J. F., Concrete, 52, No. 1, 103-4 (1944).
(6) Bogue, Robert H., “Chemistry of Portland Cement,” New
York, Reinhold Publishing Corp,, 1947.
(7) Brownmiller, L. T., J . Am. Concrete Inst., 14, 193-210, 212-13
(1943).
(8) Colony, R. J., Columbia Univ., Eng. Scientific Paper, 3 (Febru-
ary 1951).
(9) Farmer, N. W., personal communication, 1951.
(IO) Farmer, N. W., PZastics (London),4, 89 (1950).
(11) Griffiths, L. H., Soc. Chem. I n d . (London),1947, pp. 578-80
(12) Griffiths, L. H., Trans. Inst. Rubberlnd., 22,170-4, (1947).
(13) Mason, P. N., and Manning, J. F., “Technology of Plastics and
Resins,” New York, D. Van Nostrand Co., 1945.
(14) Mellor, B. B., S. M. thesis in chemical engineering, Massa-
’ chusetts Institute of Technology, 1952.
(15) Sindler, J., Mass. Inst. Technol., Chem. Eng. Dept. Papers,
186 (1916).
(16) Stern, H. J., India Rubber WorEd, 102, No. 2, 37-40 (1940).
(17) Swaze, M. A., J . Am. Concrete Inst., 19,317-31, (1950).
(18) Tereshkevitch, W., S. M. thesis in chemical engineering,
Massachusetts Institute of Technology, 1951.
(19) U. S. Dept. Interior, Bur. Reclamation, “Concrete Manual,”
5th ed., 1949.
(20) Van der Bie, C. F., India-Rubber J., 112,229 (1944).
(21) Van Gils, C. E., and Clarkson, H., India-Rubber J . , 118, 773-4,
776 (1950).
(22) Wren, W. G , I n d i a Rubber World, 99, No. 6, 29-31 (1939).
(23) Wren, W. G., Trans. Inst. Rubber Ind., 13,189-229 (1937).
RECEIVED for review April 1, 1952. ACCEPTEDDecember 22, 1952.
Presented before the Division of Industrial and Engineering Chemistry a t
the 121st Meeting of the AMERICANCHEMICAL SOCIETY,Buffalo, N. Y .