NEW STANDARDS MAKE

GREATER DEMANDS
The impact of the new EN 12004 standard on formulation
technology and raw materials for cement-based tile adhesives

D. Zweifel, R. Baumann, U.Tribelhorn

New Standards Make Greater Demands

The impact of the new EN 12004 standard on formulation technology

and raw materials for cement-based tile adhesives

D. Zweifel, R. Baumann, U.Tribelhorn

Contents

Background

Euronorm 12004 – A Synopsis

Summarised results

Proceeding Step by Step

Cement

Sand

Cellulose ethers

Alternative thickener systems

Redispersible polymer powders

Concrete slabs and tiles

Formulations for EN 12004

Experimental

Test methods
 New Standards Make Greater Demands
The impact of the new EN 12004 standard on formulation technology
and raw materials for cement-based tile adhesives
D. Zweifel, R. Baumann, U.Tribelhorn
The introduction of the new EN
standards for cement-based tile
adhesives, a product for which Dow
supplies METHOCEL* cellulose
ethers and DOW Latex Powders,
is making new demands on tile
adhesive producers. Standardisation
1 of the norms involves more strin-
gent testing, as well as specific
classifications for different tile
adhesive qualities, which results in
a real challenge in meeting the
standards.
Included in the EN 12004 standard
are two cement-based tile adhesive
classifications: C1 which outlines
general requirements, and C2 which
describes improved or additional
characteristics.These set out the
minimum requirements for impro-
ved adhesion after 28 days at room
temperature and under heat, water
and freeze/thaw storage conditions.
They also stipulate optional require-
ments for fast setting, reduced slip
and extended open time.
Sand and cement are the main
constituents of cement-bonded,
thin-bed adhesives and determine
the properties to a large extent.
However, no tile adhesive which
can be applied by the thin-bed pro-
cedure is formulated with sand and
cement alone. Numerous additives
enable an endless range of variations
in processing and end properties to
satisfy the wishes of the end user.
The need to be able to com-
pare and to classify this enor-
mous variety of products has
existed for a long time.
«Flexible adhesive», «standard
adhesive» and «fluidized bed
*Trademark of the Dow Chemical Company
mortar» are all examples of
attempts to categorise these
products. However, it has often
been the case that each region,
each country or even each
manufacturer, used different
terminology. After much
debate, the initiative for the
regulation of adhesive mortars
was finally agreed earlier this
year, and with EN 12004
coming into effect, the quality
requirements for cement-based
tile adhesives will now be
standardised Europe-wide,
replacing conflicting national
standards.
The tile adhesive formulator is
therefore faced with a stiff challenge
– that of demonstrating that his
products match the new standards
in test conditions. In order to
support their customers, the Dow
METHOCEL and DLP technical
experts have carried out a study to
quantify the influence of the nume-
rous variables of tile adhesives.This
knowledge should aid the formula-
tor to develop tile adhesives that
satisfy the requirements according
to EN 12004 (C1 and C2).
 Making Sense of Euronorm
EN 12004 – A Synopsis
The aim of the study is to provide
you with data and guidelines to
assist you when carrying out tests
on cement-based tile adhesives in
relation to compliance with EN
12004.
The following table (Page 2) provi-
des an overview of the require-
ments per classification of cement-
based tile adhesives.
The general classifications C1 and
C2 can be combined with additional
requirements (F,T, E).
2 Designations like C1T or C2TE
clearly describe the properties of
cement-based tile adhesives. Rapid
hardening adhesives (F) were not a
subject of this study.The freeze-thaw
cycle was also omitted, as manually
executed freeze–thaw yields results
with limited reproducibility.
Test method
Normal setting adhesives
Open time EN 1346
Tensile adhesion strength EN 1348
Water immersion EN 1348
Heat aging EN 1348
Freeze-thaw cycle EN 1348
Fast setting adhesives
F: Rapid hardening and
Open time (EN 1346)
Additional requirements
T: Slip
E: Extended open time
Note: Please refer to the original Std. EN 12004 as reference.This is just an interpretation by Dow.
The results of studies relating to
EN 12004 depend not only on the
adhesive being tested, but also
strongly on the type of tiles and
concrete slabs used.This fact must
be taken into consideration with
regard to the «absoluteness» of the
test results. Obviously the materials
used for the tests should meet
the specifications required by the
norms.
It is relatively simple to formulate an
adhesive which meets the C1 requi-
rement. It is not a great obstacle to
reach the required 0.5 N/mm2, but
the challenge is rather that of kee-
ping the cost as low as possible.
Aiming to omit the polymer powder
from the formulation would be
attractive from an economical point
of view but would fail, in our
Test class C1
≥ 0.5 N/mm2 after 20 min
≥ 0.5 N/mm2
≥ 0.5 N/mm2
≥ 0.5 N/mm2
≥ 0.5 N/mm 2
≥ 0.5 N/mm2 after 24 hours
≥ 0.5 N/mm2 after 10 min
≤ 0.5 mm
experience, because of insufficient
adhesion after heat aging.The
quantity of polymer powder can
be reduced when cement of higher
quality is used (Table 1).
It is far more difficult to formulate
tile adhesives meeting the C2
classification. Tensile adhesion requi-
rements of >1.0 N/mm2 represent
quite a challenge. The results of our
studies allow the following conclu-
sions to be drawn:
• The tensile adhesion strength can
be improved by the use of higher
quality cements. An important fact
to be taken into consideration is
that the increase in tensile adhe-
sion, after water immersion or
after heat aging, increases dispro-
portionately.
Test class C2
≥ 0.5 N/mm2 after 20 min
≥ 1.0 N/mm2
≥ 1.0 N/mm2
≥ 1.0 N/mm2
≥ 1.0 N/mm2
≥ 0.5 N/mm2 after 24 hours
≥ 0.5 N/mm2 after 10 min
≤ 0.5 mm
≥ 0.5 N/mm2 after 30 min
 Making Sense of Euronorm
EN 12004 – A Synopsis

• Lightly modified cellulose ethers

have limited slip resistance and a
reduced water demand but show
their advantage in the tensile
adhesion after water immersion
and heat aging.

• The loss in slip resistance can be

compensated by means of sheet
silicates and/or cellulose fibres.
The improvement in slip resistance
is often reached without a
compromise in tensile adhesion
strength.
3
• By optimising the cellulose ether it
is possible to develop slip resistant
adhesives (slip <0.5 mm) which
yield remarkable tensile adhesion
strength with a DLP 2000 addition
level of only 1% and 3% (see
Formulations 40 and 41).

• By selectively adjusting the poly-

mer powder addition level it is
possible to develop tile adhesives
meeting either C1 or C2 classifi-
cation.The newly developed
polymer powder DLP 2000 will
yield extremely high tensile
adhesion strength. If the formula-
tion is optimised just to meet
minimum requirements, then these
properties can be met with a
relatively low addition level of DLP
2000. This clearly has a positive
effect on the costs. A reduction in
the addition level from 4 to 3% or
2 to 1% respectively would result
in a reduction in cost of 10% to
15% of the total formulation.
Summary of study results

The conclusions of the study are summarised in the above figure.

The effect that each of the investigation parameters has on the
final properties is shown as an arrow pointing in the influencing
direction.
 Proceeding step by step
Cement

In order to quantify the effect of the individual components of tile

adhesives on its processing and end properties, it is appropriate,
given the large number of additives, to proceed step by step and
ingredient by ingredient.

Parts of the work were done utilising computer-aided statistically designed

experiment planning and evaluation.

Portland cement is available in many
quality classifications. Depending on
the particle size and the chemical
composition of the clinker, concrete
with different compressive strength
values is obtained. Fine particles
will hydrate better, thus yielding
5 higher strength values.This effect
can also be observed in cement-
based tile adhesives as the following
table demonstrates:
Results: The influence of the
Portland cement quality on the
tensile adhesion results is not so
evident in all tests. Changing the
Portland cement quality from CEM I
42.5 to CEM I 52.5, the standard
tensile adhesion improved only
slightly, by an average of 0.2 N/mm2.
Comparing the tensile adhesion
results in the same set of tests,
after 20 minutes and 30 minutes
open time, no difference can be
determined.
Results obtained after the water
immersion test (+0.3 N/mm2) and
after heat aging (+0.5 N/mm2)
demonstrate that the use of
better quality Portland cement
can be advantageous. Practice has
proven that the tensile adhesion,
after these two aging procedures,
are the most critical properties
in order to meet EN 12004
requirements. Surprisingly the
nominal improvement of the tensile
adhesion is independent of the
redispersible polymer powder level,
which means that the increase in
tensile adhesion strength which is
influenced by the cement quality,
is the same for both the formu-
lations containing 1% DLP 2000 and
3% DLP 2000.

Components Formulation 1 Formulation 2 Formulation 3 Formulation 4

Steidle sand Wt.-% 60 60 60 60
CEM I 42.5 Wt.-% 40 40
CEM I 52.5 Wt.-% 40 40
XCS 41120.00 Wt.-% 0.4 0.4 0.4 0.4
DLP 2000 Wt.-% 1.0 1.0 3.0 3.0
Bentone GS 1) Wt.-% 1.0 1.0 1.0 1.0
Arbocell BWW40 2) Wt.-% 0.5 0.5 0.5 0.5
Water Wt.-% 32 31 31 30

Properties
Slip mm 2.0 2.0 4.0 3.0
Tensile adhesion strength
Standard N/mm2 0.88 1.05 1.39 1.56
20 min open time N/mm 2
0.86 1.02 1.39 1.34
Water immersion N/mm2 0.70 1.02 0.69 1.01
Heat aging N/mm 2
0.15 0.65 1.00 1.50

Table 1: Comparison of two different cement qualities with two different DLP 2000 levels

1) Trademark of Rheox Europe S. A. Bruxelles

2) Trademark of Rettenmaier & Söhne, Ellwangen
 Proceeding step by step
Sand

Because of the relatively high
transport costs, the choice of sand
remains limited to local sand
supplies. Nevertheless, it makes
sense to investigate the influence of
the sand quality on the application
and final properties of tile adhesives.
In our studies we limited the
number of sands to two very
different types. Zimmerli sand is a
highly refined quality with a rather
narrow particle size distribution
(0.1 – 0.3 mm) and a very low
specific surface (< 0.1 m2/g ). In
6 contrast, Steidle sand has a broader
particle size distribution (0 – 0.45
mm) and a substantially higher
specific surface (~ 2.9 m2/g).
Results: Comparing the two
formulations, where only the sand
quality was altered, shows that the
properties obtained are almost
identical. Sand has the function of a
filler in a tile adhesive formulation.
It is therefore to be expected
that the influence on the tensile
adhesion strength remains low.
The sand with the higher specific
surface required two parts more
water in order to maintain the
same slip and consistency.
Ground limestone (~60 µm) is often
added to the formulation as a fine
filler to improve the application
properties and a better optical
appearance of the liquid mortar.
Formulation 7 (table 2) proves that
the use of ground limestone in
moderate amounts does not harm
the end properties of a tile
adhesive. Excessive amounts of
ground limestone, however, have a
detrimental effect on open time.

Components Formulation 5 Formulation 6 Formulation 7

Steidle sand Wt.-% 60 55
Zimmerli sand Wt.-% 60
Limestone 60 µm Wt.-% 5
CEM I 52.5 Wt.-% 40 40 40
METHOCEL 10-0350 Wt.-% 0.5 0.5 0.5
DLP 2000 Wt.-% 2.0 2.0 2.0
Water Wt.-% 28 26 28

Properties
Rheology
BF 0.5 rpm mPa·s 3,971,000 3,793,000 4,298,000
BF 5.0 rpm mPa·s 557,000 528,000 570,000
BF 50 rpm mPa·s 91,000 84,000 94,000
Slip mm 0.5 0.5 0.5
Tensile adhesion strength
Standard N/mm2 1.16 1.19 1.08
20 min open time N/mm2 1.56 1.59 1.59
30 min open time N/mm 2
1.03 1.27 1.02
Water immersion N/mm 2
0.43 0.61 0.54
Heat aging N/mm 2
0.94 1.00 0.87

Table 2: Different sand qualities in tile adhesive formulations

 Proceeding step by step
Cellulose ethers

Cellulose ethers are among the
most important additives in a tile
adhesive formulation.These additives
substantially affect application and
end properties. Cellulose ethers are
not only thickeners, controlling
water demand and water retention,
but also through the degree of
modification and their rheological
effect, they determine the tensile
adhesion strength, slip resistance,
open time and application proper-
ties.
7 The following table demonstrates
the influence of different cellulose
ether types on the properties of
a tile adhesive.
Results: METHOCEL 10-0356 is a
modified cellullose ether with a
pronounced thickening effect.
METHOCEL 10-0350 has a compa-
rable viscosity (~10 000 mPa·s)
mode-rately modified, and experi-
mental celluose ether XCS
41120.00 is even less modified. In
the test series (Table 3) the water
level was adjusted in order to obtain
approx. 400 000 mPa·s (5.0 rpm).
Depending on the degree of
modification the water demand
changed accordingly.The slip
resistance decreases with water
demand, which can be explained by
the lower structural viscosity of the
liquid mortar. The structural visco-
sity is a measure of how much the
viscosity decreases with increasing
shear rate. As a measure of the
structural viscosity, the difference of
the logarithm of the viscosity
determined at 0.5rpm and 50rpm,
is used.With the exception of the
results after hot aging, the tensile
adhesion results are comparable.
Reducing the degree of modification
appears to have a positive effect on
the tensile adhesion after heat aging.
The tensile adhesion after heat
aging represents in many cases the
most critical obstacle to fulfilling
EN 12004.The slip resistance and
the water demand are negatively
influenced by a lower degree of
modification. One way out of this
dilemma would be an additive that
increases the water demand and
slip resistance, without having a
negative impact on tensile adhesion,
especially after hot aging.

Components Formulation 8 Formulation 9 Formulation 10

Zimmerli sand Wt.-% 60 60 60
CEM I 42.5 Wt.-% 40 40 40
METHOCEL 10-0356 Wt.-% 0.4
METHOCEL 10-0350 Wt.-% 0.4
XCS 41120.00 Wt.-% 0.4
DLP 210 Wt.-% 4.0 4.0 4.0
Water Wt.-% 28 26 25

Properties
Rheology
BF 0.5 rpm mPa·s 3,750,000 2,780,000 2,100,000
BF 5.0 rpm mPa·s 416,000 396,000 384,000
BF 50 rpm mPa·s 55,000 76,000 76,000
log (0.5 rpm) – log (50 rpm) 1.83 1.56 1.45
Slip mm 0.5 1.5 2.0
Tensile adhesion strength
Standard N/mm2 1.25 1.32 1.45
20 min open time N/mm 2
1.19 1.35 1.25
30 min open time N/mm2 0.69 0.72 0.75
Water immersion N/mm 2
0.68 0.73 0.76
Heat aging N/mm 2
0.34 0.58 0.80

Table 3: Property profile of cellulose ethers in cement based tile adhesives

 Proceeding step by step
Alternative tickener systems

It was found that other, non
water-soluble thickeners increase
the consistency of cement-based
tile adhesives, without negative
consequence on the tensile adhe-
sion. Sheet-silicates and cellulose
fibres are such products.
Results: Table 4 clearly demonstra-
tes that it is possible to increase the
water demand of a tile adhesive for-
mulation with the aid of sheet
silicates (Pangel S-9) or cellulose
fibres (Arbocel BWW 40) without
reducing the slip resistance. Even
more important is the fact that the
tensile adhesion does not deterio-
rate by the addition of these types
of additives.

8 Components Formulation 11 Formulation 12 Formulation 13

Steidle sand Wt.-% 60 60 60
CEM I 52.5 Wt.-% 40 40 40
METHOCEL 10-0350 Wt.-% 0.5 0.5 0.5
Pangel S-9 3) Wt.-% 0.5
Arbocell BWW 40 Wt.-% 0.5
DLP 2000 Wt.-% 2.0 2.0 2.0
Water Wt.-% 28 32 32

Properties
Rheology
BF 0.5 rpm mPa·s 3,790,000 3,201,000 2,960,000
BF 5.0 rpm mPa·s 594,000 464,000 436,000
BF 50 rpm mPa·s 96,000 79,000 73,000
Slip mm 1.0 0.75 1.0
Tensile adhesion strength
Standard N/mm2 1.19 1.31 1.20
20 min open time N/mm 2
1.69 1.44 1.35
30 min open time N/mm 2
1.27 1.10 1.28
Water immersion N/mm2 0.85 0.96 1.01
Heat aging N/mm 2
0.89 1.22 1.21

Table 4: Alternative thickeners for cement-based tile adhesives

3) Trademark – Grupo Tolsa, Madrid

 Proceeding step by step
Alternative tickener systems

Results: Bentone GS, a hectorite
and Optibent CP, a bentonite, have
nearly the same effect on the tensile
adhesion properties. Optibent CP
increases the viscosity to a lesser
degree than Bentone GS.
Attapulgites, such as Minugel 200
increase the consistency, but they
have a negative influence on tensile
adhesion properties. In particular,
the open time and the adhesion
after the heat aging deteriorate.
Pangel S9, a sepiolite has proven to
be most effective.The thickening
effect is twice as efficient as
hectorite or bentonite. In practice
this means that only half the dosage
level is required to reach the same
viscosity.The tensile adhesion is
not influenced and remains high.

Components Formulation 14 Formulation 15 Formulation 16 Formulation 17

9 Steidle sand Wt.-% 60 60 60 60
CEM I 42.5 Wt.-% 40 40 40 40
XCS 41120.00 Wt.-% 0.4 0.4 0.4 0.4
DLP 210 Wt.-% 4.0 4.0 4.0 4.0
Bentone GS Wt.-% 1.0
Minugel 200 4) Wt.-% 1.0
Optibent CP 5) Wt.-% 1.0
Pangel S-9 Wt.-% 0.5
Water Wt.-% 28 28 28 28

Properties
Rheology
BF 0.5 rpm mPa·s 3,600,000 3,974,000 2,690,000 3,290,000
BF 5.0 rpm mPa·s 528,000 598,000 478,000 440,000
BF 50 rpm mPa·s 93,000 100,000 85,000 77,000
Slip mm 1.0 1.0 1.0 0.5
Tensile adhesion strength
20 min open time N/mm2 1.95 1.41 1.90 1.32
30 min open time N/mm 2
0.99 0.48 1.07 0.94
Water immersion N/mm2 0.84 0.74 0.85 0.81
Heat aging N/mm 2
0.90 0.64 0.94 0.79

Table 5:The effects of different sheet silicates on the properties of a tile adhesive.

4) Trademark of ITC, Inc. Maryland, USA

5) Trademark of Südchemie AG, Munich
 Proceeding step by step
Redispersible polymer powder
Redispersible polymer powders are
crucial components of high quality
tile adhesive formulations.These
additives substantially increase the
tensile adhesion and improve the
flexibility of the adhesive link
between the tile and the substrate.
This feature is very important
especially with difficult substrates
like wood, old tiles and when floors
are equipped with floor heating.
Redispersible polymer powders also
play a key role in tile adhesives
meeting EN 12004.
10
The figure below illustrates the
effect of two different polymer
powders on the tensile adhesion
properties of a tile adhesive. Both
products are vinyl acetate/ethylene
based. However, DLP 2000 is a
harder polymer with a higher glass
transition temperature than
DLP 210.
2.5
2
Tensile adhesion, N/mm2
1.5
1 Zimmerli-Sand
0.5
0
w/o
Figure 1: Comparison of two DLP products in a tile adhesive formulation at two addition levels.
Results: A rather simple base for-
mulation with a low water demand
was used.This explains the relatively
low tensile adhesion values obtai-
ned. However, the influence an
increased powder level has on the
properties in other formulations,
can be estimated accordingly.
Without addition of polymer pow-
ders the tensile adhesion after heat
aging has almost completely collap-
sed.The standard tensile adhesion,
as well as the tensile adhesion after
heat aging, improves when the level
of polymer powder is increased.This
effect is more pronounced with DLP
2000.
When cement of better quality is
used or if other rheological additives
(sheet silicates, cellulose fibres) are
added to increase the water
demand it is possible to achieve
tensile adhesion values with DLP
DLP 210
2% 4% 6% 2% 4%
DLP
2000, which fulfill the requirements
of EN 12004/C2.
As demonstrated in the previous
simple formulation, here too in
Figure 2 an increase in the polymer
powder addition level shows a clear
improvement in the standard tensile
adhesion, as well as in the tensile
adhesion after heat aging.
Apparently, the addition level of
polymer powder has no influence
on the tensile adhesion after water
immersion. In this formulation the
addition of only 2% of DLP 2000
is sufficient to achieve a tensile
adhesion of 1.0 N/mm2 after
standard, wet and heat aging.
Figure 3 shows the results of
deformation measurements of cured
adhesive strips according to EN
12002. It is remarkable to see that
the maximum transversal defor-
mation more than doubles with the
DLP 2000
Standard
Heat aging
Water imm.
Base formulation:
60.00 Wt. – %
CEM I 42.5 40.00 Wt. – %
XCS 41120.00 0.45 Wt. – %
Water 25.00 Wt. – %
6%
 Proceeding step by step
Redispersible polymer powder

1.8
Tensile adhesion strength, [N/mm2]

Base formulation 1% DLP 2000

1.6 Steidle sand 60.0 Wt. – % 2% DLP 2000
CEM I 52.5 40.0 Wt. – % 3% DLP 2000
1.4 XCS 41120.00 0.4 Wt. – %
Bentone GS 1.0 Wt. – %
Arbocell BWW40 1.5 Wt. – %
1.2

0.8

0.6

11
0.4

0.2

0
Standard Water immersion Heat aging

Figure 2: Influence of addition level on tensile adhesion

Deformation with different Polymer powders according to EN 12002

10
Deformation (L)
Force (F)

Base formulation
Deformation (mm)

Zimmerli sand 60 Wt. – %

Force (N)

CEM I 42.5 40 Wt. – %

10-0366 0.45 Wt. – %
5 Polymer powder 0-6 Wt. – %
Water 25 Wt. – %

0
0% 2% 4% 6% 2% 4% 6%
DLP 210 DLP 210 DLP 210 DLP 210 DLP 2000 DLP 2000 DLP 2000

Polymer powder type and addition level

Figure 3: Maximum transversal deformation and maximum force of a tile adhesive formulation containing two different types of polymer powders
 Proceeding step by step
Redispersible polymer powder

increasing polymer powder level,
whereas the maximum force
remains at a similar level.
The performance with regard to
maximum deformation and force of
DLP 210 and DLP 2000 are very
similar.
The choice of the optimum polymer
powder is important to the overall
performance of the tile adhesive
such as open time, standard tensile
adhesion, tensile adhesion after
specified aging procedures, and
rheological properties. Depending
on the property profile desired,
which also depends on the other
components of the formulation
(e.g. sand, cement, cellulose ether),
the redispersible polymer powder
must be carefully selected to fit the
formulation.

Application properties of different polymer powders

Components Formulation 26 Formulation 27 Formulation 28 Formulation 29

12 CEM 42.5 Wt.-% 40 40 40 40
Steidle sand Wt.-% 60 60 60 60
10-0350 Wt.-% 0.5 0.5 0.5 0.5
Std.VA / E Type Wt.-% 3
DLP110 Wt.-% 3
DLP210 Wt.-% 3
DLP 2000 Wt.-% 3
Water Wt.-% 28 28 28 28

Properties
Density kg/m3 1543 1462 1500 1537
Rheology
BF 0.5 rpm mPa·s 3,132,000 3,713,000 3,324,000 3,587,000
BF 5 rpm mPa·s 445,000 457,000 453,000 467,000
BF 50 rpm mPa·s 71,000 77,000 74,000 75,000
Slip mm 1.2 1.5 1.6 1.0
Tensile adhesion strength
Standard N/mm2 1.21 1.47 1.04 1.20
10 min open time N/mm 2
1.70 1.83 1.73 1.96
30 min open time N/mm2 1.54 1.18 1.38 1.92
Heat aging N/mm 2
0.57 0.39 0.38 0.74
Water immersion N/mm 2
0.18 0.79 0.67 0.69

Table 6: Comparison of different polymer powders

 Proceeding step by step
Redispersible polymer powder

Identification Polymer base Flexibility Tg (C) MFT

Std.VA / E type Wt.-% VA/E Hard 17 0
DLP 110 Wt.-% VA/Veova Hard 22 4
DLP 210 Wt.-% VA/E Soft 6 0
DLP 2000 Wt.-% VA/E Medium hard 17 3

VA: Vinyl acetate E: Ethylene VeoVa: Vinyl ester of versatic acid

Table 6 shows the properties of the tensile strength after water

different redispersible polymer
powders in a standard tile adhesive
13 formulation. DLP 110, a relatively
hard VA/VeoVa grade proves its
advantage in the standard tensile
adhesion and in the tensile adhesion
after water immersion.The tensile
adhesion after 30 min open time is
lower compared with other
polymers.VA/VeoVa polymers tend
to show skin formation after
a longer open time.
The standard VA/E copolymer shows
a balanced standard tensile strength
and open time properties. However
immersion is lower (0.18 N/mm2)
compared with all other polymers
used.The tensile strength of DLP
210 is somewhat lower after heat
aging compared to the Std.VA/E
copolymer. After the water immer-
sion, however, it is clearly better
(0.67 N/mm2).The medium hard
DLP 2000 shows a very balanced
performance between standard
tensile adhesion, open time and
adhesion after heat aging and water
immersion. It outperforms all other
polymers tested in most of the
properties.
 Proceeding step by step
Concrete slabs and tiles

The test results obtained do not
only depend on the composition of
the tile adhesive, but also on the
quality of the substrate, namely the
concrete slabs and the tiles onto
which the adhesive is applied.The
quality of the concrete slabs
depends on various parameters
like the nature of the surface, the
absorption behaviour and the
thermal expansion coefficient.
4 hours. For practical and econo-
mical reasons, commercially available
concrete slabs are used for testing.
Slabs fulfilling EN 1323 requirements
are not available at reasonable cost.
For the study, we had two qualities
of concrete slab at our disposal.
Neither of the slabs fulfills the EN
Water absorption according
to EN 1323
1323 requirement of 0.5 – 1.5 ml
water absorption. Slab A absorbs
substantially more water, whereas
slab B absorbs practically no water.
This behaviour has serious conse-
quences for the tensile adhesion
results obtained, as the following
table demonstrates.

EN 1323 specifies water absorption Slab A 2.0 – 3.5 ml

limits of 0.5 – 1.5 ml within the first Slab B 0.05 – 0.20 ml
14

Components Formulation 30 Formulation 31 Formulation 32 Formulation 33

Concrete slab A B A B
CEM 42.5 Wt.-% 40 40 40 40
Zimmerli sand Wt.-% 60 60 60 60
METHOCEL 345 Wt.-% 0.5 0.5
10-0350 Wt.-% 0.5 0.5
DLP 210 Wt.-% 2 2
Water Wt.-% 28 28 28 28

Properties
Rheology
BF 0.5 rpm mPa·s 2,112,000 2,112,000 3,511,000 3,511,000
BF 5 rpm mPa·s 465,000 465,000 447,000 447,000
BF 50 rpm mPa·s 101,000 101,000 71,000 71,000
Tensile adhesion strength
10 min open time N/mm2 1.08 1.56 1.06 1.49
30 min open time N/mm 2
0.10 0.36 0.92 1.45
Heat aging N/mm 2
0.10 0.80 0.43 0.94
Water immersion N/mm 2
0.86 0.90 0.82 0.94

Table 7: Tensile adhesion strength obtained with two types of concrete slabs
 Proceeding step by step
Concrete slabs and tiles

Results: The tensile adhesion
results obtained with the more
absorbing concrete slabs (A) are in
this case lower than with the less
absorbing concrete slabs (B). Only
the values obtained after the water
immersion remain independent of
water absorption.The largest
difference in the results obtained
with the two different slabs was in
tensile adhesion strength after heat
aging, where values varied by a
factor of two to eight. Hence a
correlation between water absorp-
15 tion and tensile adhesion strength
could be established.
The difference in the results obtai-
ned after 10 and 30 minutes open
time can be explained by the lack of
water retention.The adhesive
applied onto the more absorbent
concrete slab dries out more until
the tile is inserted.The differences
obtained after heat aging are
difficult to estimate and are there-
fore the subject of further investiga-
tion.The test results of formulation
30/31 demonstrates that the
C1 classification can also be met
without redispersible polymer pow-
der depending on the substrate
used (heat aging value).
In all our studies we used concrete
slab type A. Even though it does not
meet the EN 1323 requirements,
the slab yielded reproducible results.
The fact, that the results with these
slabs were lower, only indicates
tougher test conditions, which
should not diminish the quality of
the work described.
The quality of the tiles influences
the performance of a tile adhesive in
a similar way to that already seen
with the concrete slabs. In the
following table the influence of fully
vitrified tiles and porous tiles (from
two different tile producers), on the
tensile adhesion, is demonstrated.
The data show the influence of
different tile types on the adhesion
performance using two different tile
adhesive formulations. A rather
simple tile adhesive formulation

Components Form 34 Form 35 Form 36 Form 37 Form 38 Form 39

CEM 42.5 Wt.-% 40 40 40 40 40 40
Steidle sand Wt.-% 60 60 60 60 60 60
METHOCEL 267 Wt.-% 0.5 0.5 0.5
METHOCEL 10-0350 Wt.-% 0.5 0.5 0.5
Water Wt.-% 30 30 30 30 30 30
Tile type:
Porous tile, EN 159 X X
Fully vitrified French tile, EN 176 X X
Fully vitrified German tile, EN 176 X X

Properties
Tensile adhesion strength
10 min open time N/mm2 1.32 0.91 1.16 1.34 0.93 1.09
30 min open time N/mm 2
0.54 0.39 0.62 0.70 0.52 0.67
Heat aging N/mm2 0.46 0.07 0.11 0.38 0.00 0.03
Water immersion N/mm2 1.15 0.70 1.16 1.07 0.67 1.08

Table 8: Comparison of different tiles

 Proceeding step by step
Concrete slabs and tiles

based on CEM I 42.5 and two

different types of cellulose ether
were compared. None of these for-
mulations contain polymer powder.

The influence of tile quality on adhe-

sion was most pronounced after
heat aging.The tensile adhesion
obtained with the porous tile was
0.46 N/mm2 and 0.38 N/mm2, where
as a tensile adhesion of only 0.07
N/mm2 was obtained with the fully
vitrified (EN 176) tile from France.
Tensile adhesion using the second
16 formulation was totally lost.

The fully vitrified German tile (EN

176), showed only marginally better
performance after the heat aging.
However, the open time and the
tensile adhesion after water immer-
sion with this tile were similar to
the results of the porous tile and
clearly better than the results obtai-
ned with the fully vitrified French
tile.This demonstrates that different
adhesion performance results can be
obtained with different tiles, meeting
the same norm (EN 176).Why such
differences arise may depend, for
instance, on the porosity, surface
nature, or on the thermal behaviour.
In order to keep conditions con-
stant we only used the French fully
vitrified tiles for all our studies
according to EN 1348.
 Development of formulations for
the EN 12004 classification

The purpose of this part of the
study was to optimise tile adhesive
formulations to meet a C1T/C2TE
classification as cost effectively as
possible.With the help of a com-
puter aided experimental design
software program (JMP) the
influence of the following parame-
ters were investigated: nominal
viscosity of the cellulose ether,
degree of modification as well as
addition level of cellulose ether
and polymer powder.
Results:The results from this
evaluation allow the following con-
clusions, which could be specific to
the raw materials used (Steidle sand,
CEM I 52.5):
The low viscosity cellulose ether
(4000 mPa·s) has an advantage in
open time, where the tensile adhe-
sion was more than 40% higher.
A cellulose ether concentration of
0.4% also yielded improved adhesion
after heat aging (+15%).
A medium to strong modification
of the cellulose ether improves the
open time particularly.The latter
also has a strong influence on the
water demand, which can be
increased by 3% whilst maintaining
the slip resistance.The addition
level of DLP 2000 has a great
influence on the adhesion results
after heat aging.

17
Impact of formulations parameters on the properties of the tile adhesive:

Formulation CE-Viscosity CE-Dosage CE- DLP 2000

parameters Modification Dosage
Adhesives
properties

Water demand

Standard
adhesion

20 min open
time

30 min open
time

Heat aging

Water
immersion

Table 9: Dependence of the variables as calculated by JMP

 Development of formulations for
the EN 12004 classification

The water level can also be reduced

by 1% with every additional 1% of
DLP 2000 whilst maintaining the
same slip resistance.

As a result of the experimental

design an optimum formulation
(Table10, Formulation 40), can be
developed meeting the C1T classifi-
cation e.g. <0.5 mm slip, 0.5 N/mm2
tensile adhesion strength after all
aging procedures. Even the optional
requirement for prolonged open
time is achieved (0.5 N/mm2 after
18 30 minutes). Analogous to the
development of a C1T formulation,
a further formulation for C2TE is
shown in Table 10, Formulation 41,
where 1.0 N/mm2 tensile adhesion
strength after aging procedures as
well as 0.5 N/mm2 after 30 min.
open time have to be met.With the
exception of the tensile adhesion
after the water immersion, the
requirements can be met with the
addition of only 3% DLP 2000.
Formulation 42 meets the C2TE
classification with a higher modified
cellulose ether XCS 41405.00.This
is possible at an elevated water level
of 30% with only 2% of redispersible
polymer powder.
Cellulose ether XCS 41406.00 is
used in formulation 43 which meets
the C2TE classification at a water
level of 32%.
 Development of formulations for
the EN 12004 classification

Components Formulation 40 Formulation 41 Formulation 42 Formulation 43

CEM 52.5 Wt.-% 40 40
CEM 52.5 Milke Wt.-% 40 40
Steidle sand Wt.-% 60 60 60 60
Cellulose ether XCS 41142.00 Wt.-% 0.4
Cellulose ether XCS 41403.00 Wt. -% 0.5
Cellulose ether XCS 41405.00 Wt. -% 0.5
Cellulose ether XCS 41406.00 Wt. -% 0.5
Degree of modification Medium Medium Medium-high High
DLP 2000 1 3 2 3
19 Water Wt.-% 27 27 30 32

Properties
Density kg/m3 1510 1544 1580 1650
Rheology
BF 0.5 rpm mPa·s 2,905,000 4,318,000 3,206,000 2,985,000
BF 5 rpm mPa·s 445,000 875,000 544,500 352,000
BF 50 rpm mPa·s 82,000 141,000 79,000 49,000
Slip mm 0.5 0.5 0.5 0.5
Tensile adhesion strength
Standard N/mm2 0.92 1.26 1.16 1.37
20 min open time N/mm 2
1.44 1.17 0.98 1.64
30 min open time N/mm2 0.85 0.53 0.99 1.56
Heat aging N/mm 2
0.52 1.17 1.13 1.04
Water immersion N/mm 2
1.09 0.93 1.00 1.08
meeting EN 12004 classifications C1T C1TE+ C2TE C2TE

Table 10: Formulations of three experimental designs

 Experimental

Raw materials

Cement

Identification Classification Manufacturer

Normo 4 CEM I 42.5 HCB Siggental, Switzerland
Normo 5 CEM I 52.5 HCB Siggental, Switzerland
Milke cement CEM I 52.5 R Milke Geske, Germany

Sand

Zimmerli Sand Steidle Sand

20
Specific surface: <0.1 m /g
2
Specific surface: 2.885 m2/g
Volume % Particle size [µm] Volume % Particle size [µm]
10 130 15 80
40 180 10 110
40 230 10 140
10 280 15 80
20 230
20 280
10 360

Cellulose ethers (typical product properties)

Identification Viscosity [Brookfield RVT, 20 rpm, 2% soln. ] Degree of modification

METHOCEL 10-0356, cellulose ether 10,000 mPa·s High
METHOCEL 10-0350, cellulose ether 10,000 mPa·s Medium-high
METHOCEL 10-0366, cellulose ether 10,000 mPa·s Low
Exp. cellulose ether XCS 41120.00 7,000 mPa·s Low
Exp. cellulose ether XCS 41142.00 4,000 mPa·s Medium
Exp. cellulose ether XCS 41403.00 4,000 mPa·s Medium
Exp. cellulose ether XCS 41405.00 4,000 mPa·s Medium-high
Exp. cellulose ether XCS 41406.00 4,000 mPa·s High

Redispersible polymer powder (typical product properties)

Identification Polymer Bulk density [g/dm3] Ash content [%] MFT [°C] Tg [°C]
DLP 210 PVAc/E 425 10 0 6
DLP 2000 PVAc/E 450 10 2 17
DLP 110 PVAc/VeoVa 450 10 4 22
 Experimental

Sheet silicate

Identification Mineralogical description Manufacturer

Pangel S-9 Sepiolite Grupo Tolsa, Madrid
Bentone GS Hectorite Rheox Europe S.A., Bruxelles
Optibent CP Bentonite Süd-Chemie AG, Munich
Minugel 200 Attapulgite ITC, Inc., Maryland, USA

Cellulose fibre

Identification Manufacturer Fibre length [(m] Fibre diameter [µm]

21
Arbocell BWW 40 J. Rettenmaier & Söhne 200 20

Concrete slabs

Identification Manufacturer/Supplier Dimensions [m] Water absorption

l x w x t EN1323
Concrete flagstones Antoniazzi, Italy 0.4 x 0.4 x 0.04 0.05 – 0.20 ml
Concrete flagstones Baubedarf, Horgen 0.5 x 0.25 x 0.04 2.00 – 3.50 ml

Tiles

Identification Manufacturer/Supplier Dimensions [mm] Standard

Ostara Laufen Ostara 50 x 50 x 5 cut EN 159
Uni blanc Winckelmans 50 x 50 x 5 EN 176
Villeroy Boch 47 x 47 x 3 EN 176
 Test methods

Consistency measurement

A Brookfield Viscometer equipped with a Helipath spindle was used to

determine the consistency (viscosity) of the liquid tile adhesive mortar.
The consistency was measured at three shear rates (0.5, 5.0 and 50 rpm).
In addition to rotating, the spindle oscillated up and down, to avoid shear
aging of the liquid mortar.

Testing of all adhesive formulations were carried out according to the

Euro-Norm:

Slip fully vitrified tiles (EN 176) 100x100 mm;
EN 1308 200g loaded with 50 N for 30 seconds
slip determined after 20 minutes
Open time porous tiles (EN159) 50x50 mm loaded
EN 1346 with 20 N for 30 seconds; insertion time
after 10, 20, and 30 minutes tensile
22 adhesion test after 28 days; the insertion
time at which the tensile adhesion still
exceeds 0.5 N/mm2 is determined
Tensile fully vitrified tiles (EN 176) 50x50 mm
adhesion loaded with 20 N for 30 seconds;
EN 1348 insertion time within 5 minutes after
mortar application determination of the
tensile adhesion strength after 28 days
Heat aging fully vitrified tiles (EN 176) 50 x 50 mm
EN 1348 loaded with 20 N for 30 seconds;
insertion time within 5 minutes after
mortar application determination of the
tensile adhesion strength after 14 days
standard climate and 14 days at 70°C
Transverse determination of the transverse defor-
deformation mation of tile adhesives and grouts:
EN 12002 The maximum deflection and the maxi
mum stress of a (280 x 45 x 3mm)
mortar strip is determined after curing
for 14 days in a polyethylene bag and
14 days at standard climate conditions

Water fully vitrified tiles (EN 176) 50 x 50 mm

immersion loaded with 20 N for 30 seconds;
EN 1348 insertion time within 5 minutes after
mortar application determination of the
tensile adhesion strength after 7 days
standard climate and 20 days water
immersion
For more information about METHOCEL cellulose ethers and DLP redispersible polymer powders contact DOW at:
Telephone: international +800 3694 63 67, Fax: international +32 34 50 28 15
Website: www.methocel.com, email: dowcig@dow.com

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