Quelle/Publication: European Coatings Journal

Ausgabe/Issue: 10/2006
Seite/Page: 30

Winning time
APP plays an important role in intumescent coatings. Its
New developments in intumescent paints for reaction with the other components takes place at around
structural-steel protection. 250°C to form a thermally insulating carbonaceous char.
The need for fire resistant coatings for structural steel in The char can be expanded up to 50 times the original
modern architecture is increasing. Ammonium thickness of the coating. This layer reduces the rate of
polyphosphate is an environmentally friendly and versatile heating of the steel and prolongs its load bearing capacity.
flame retardant which is used in modern steel protective The combined use of steel construction methods and
coatings. Improved, polymer coated ammonium intumescent fire protection has proved the most cost
polyphosphate grades together with new technologies such effective and reliable solution in many different situations.
as ceramifying agents will widen the existing range of Although steel does not burn, it looses stability at
applications in architecture and offer a considerably higher temperatures above 550°C. The consequences of this effect
safety standard. were catastrophically seen in the collapse of the World
Thomas Futterer, David Garcia, Vicens Mans, Hans-Dieter Trade Center due to the high temperatures of the fires. The
Nägerl, Eduardo Tortosa. rate of heating of steel can be greatly reduced by the use of
The ammonium salts of orthophosphoric acid, MAP and insulating materials such as an intumescent coatings, which
DAP, have been used as additives for flame retardants (FR) increases the time until the steel reaches its critical
for decades. They have also been used in coatings for temperature. The primary objective is the prevention of
construction elements, mainly made from steel, wood, and structural steel collapse, which in turn will win valuable time
other building materials. Because of their high solubility and and possibilities for the escape of the occupants and ensure
low thermal stability, however, the application of these the safety of rescue services.
products in modern architectural applications, where higher
standards apply, is very limited. How do intumescent coatings operate?
Intumescent coatings contain four basic "synergistic"
Halogen-free polyphosphates find wider use ingredients:
Ammonium polyphosphate (APP, FR CROS 484) is the 1. a catalyst, i.e. a dehydrating or carbonising agent, such
ammonium salt of polyphosphoric acid. In contrast to MAP as APP, which at temperatures above 200°C liberates
and DAP, it has a polymeric structure with the general polyphosphoric acid
formula [NH3 · HPO3]n (Figure 1). APP is an efficient and 2. a source of carbon, i.e. organic substances which can be
multi-purpose FR, which is widely used. charred and turned into coal-like products by polyphosphoric
Due to the environmental and toxicological concerns acid, for example polyols such as pentaerythritol or
surrounding many halogenated products, FRs based on dipentaerythritol.
APP, which are halogen-free, are finding a broader range of 3. a blowing agent such as melamine, which under
uses. Especially in construction and building, APP is playing decomposition releases gases (N2, NH3) which expand the
a mayor role as flame-retardant additive in intumescent char.
paints for the fire protection of structural steel. 4. a binder/resin system, for instance acrylic resins, epoxy
Two crystal forms of APP (APP I and APP II) are resins etc.
commercially available and used as major ingredients for Typical formulations of solvent or water based intumescent
fire-retardant coatings. APP I has a chain length of about coatings are given in Table 1.
100, and that of APP II is more than 1,000. APP II is finding
more applications than APP I, because of its better water Coated APP grades yield higher weathering resistance
resistance and higher thermal stability in paints and New coated grades have been developed in which the APP
coatings, especially for exterior applications. II particle is surface treated with different resins, plastic
APP II decomposes at temperatures above 280°C. materials or agents. Various coating methods can be used,
Ammonia is released and the remaining polyphosphoric acid such as adhesion, ionic bonding or covalent bonding. For
forms a melted, glassy surface. In water, APP is slowly instance, APP II can be coated with amines, amino resins
hydrolysed to MAP. (shell-coated or reaction-coated), silanes (reaction-coated or
Large amounts of standard APP II are used worldwide in coating by adhesion), but also with silicones, thermosets or
industrial coatings for fire protection of structural steel. New thermoplastic resins.
building regulations, such as ENV 13381-4, with stronger Materials which have a low but significant water solubility,
requirements and more severe fire-testing conditions require such as APP, can be washed out over time. Coating of APP
APP grades that have even better fire performance, lower was found to be a very efficient method of getting around
water solubility and better compatibility to new resin and this problem. This solution is especially advantageous for
coating systems. paints and coatings that are applied on steel for external
use, where humidity can be high and persistent. Coated
Preventing or retarding structural steel collapse APP grades will remain much longer in the protection layer
Intumescence is the result of a sequential chemical reaction (Figure 2) and thus the flame retardant properties can be
between several chemical products activated by the heat of guaranteed for a longer period.
flames during the fire. Intumescent products are those which Weathering tests of three basic paints, where the only
expand (or intumesce) to several times their original size difference was the type of APP used (A, B, C: water based,
when activated by high temperatures. The final result of the and D, E, F: solvent based), were performed. The behaviour
chemical reaction is a foam that isolates and protects the of the standard APP ("FR CROS 484") versus the coated
underlying material from fire and oygen and reduces the grades ("FR CROS 487" and "FR CROS 489") was
smoke and the heat transmission. As the name implies, observed (Figure 3). Painted steel laminates of 15 x 15 cm
intumescent coatings swell up when exposed to higher with a dry film thickness of 1000 microns without top
temperatures and for example build up a thick insulation coatings were tested in a weathering chamber at a relative
layer around a steel beam. moisture of 100% and at 70°C for two days. The blistering

Vincentz Network +++ Schiffgraben 43 +++ D-30175 Hannover +++ Tel.:+49(511)9910-000

 Quelle/Publication: European Coatings Journal
Ausgabe/Issue: 10/2006
Seite/Page: 30

and weight loss of the samples were assessed. titanium dioxide 16.7%
In both systems, water- and solvent-borne paints, the coated special ceramifying additive 23.8%
APP grades reduce the weight loss and improve the surface The ceramifying additives tested were salts of phosphoric
defects. The best result was achieved with the reacted acid and others. Mixtures of one gram of the above
coated APP grades, where the weight loss was lowest. formulations were put on a steel plate, placed in an electric
furnace and heated according to the ISO curve up to 850°C
A more uniform intumescence with coated APP grades (approx. 30 minutes). Only certain materials showed a
The intumescent behaviour of all paints, A to F, was tested "ceramifying effect", which can be characterised by a harder
using a small scale test furnace consisting of a propane and more compact intumescent char. A visualisation of this
burner. This method has proved to be an excellent way of effect is shown in Figure 4. Three "ceramification"
studying char evolution and its cellular structure. The categories were defined: "Good" (hard intumescence),
following parameters were measured (Table 2): "Regular" (semi-hard intumescence) and "Bad" (soft
- Intumescence thickness intumescence). Not all salts and combinations gave good
- Cellular char structure results and improved the hardness of the intumescence
- Temperature curves versus time (Table 3).
Water based paints (A-C) generally show a higher
intumescence than solvent based (D-F) paints. Interestingly, Ceramified intumescent layers are mechanically stable
it was found that the use of coated APP grades lowered the The efficiency of all intumescent systems with positive
thickness of the intumescence, but the cell structure is more ceramifying effects was tested in a solvent-based
uniform and closed, with no cracking. Accordingly, the formulation by using a small scale test consisting of direct
temperature rise of the steel during the fire test is lower heating by a propane burner and determination of the time
when paints with coated grades are tested. This leads to a vs. temperature curves (Figure 5, salts 1, 3 and 5). A steel
better insulation and structural stability of the foamed layer plate 140 x 140 x 10 mm, cleaned by sand blasting, was
and finally to a better steel protection under high coated with one layer of a primer. The primer was applied by
temperature conditions. brushing and had a film thickness of 50-60 microns.
The fire resistance test was also performed with the Afterwards, several layers of the intumescent paint with an
weathered samples (Table 2). The results show that the total thickness (dry) of 1400-1500 microns were applied.
intumescence and heat insulation were always better when The coated specimens were dried for 30 days at room
coated APP grades were used in the paint formulation, temperature before the burning test. The fire resistance test
because of their better humidity resistance. Coated APP was performed in an electrical furnace according to ISO
grades therefore can contribute to more durable 834. The starting temperature was 25°C. The temperature
intumescent coatings which give longer and better was increased slowly and the test was stopped when the
performance, especially under high humidity and outdoor temperature reached 550°C The temperature was measured
conditions. by a thermocouple in the steel.
The paint without any ceramifying agent produced a very
pH-adjustment for better compatibility soft intumescent foam. Even when small weights (100 g)
Coated APP grades also offer a higher thermal stability with were applied, the cellular structure of the foam collapsed
a 2 % weight loss at temperatures over 300°C, measured by under the weight. In contrast, the coating formulation with
TGA. Such materials are less sensitive to shear forces ceramifying agents (salts 1 and 5) produced a thinner, but
during mixing and allow users a greater flexibility and faster much harder intumescence foam. A weight of one kilo
processes. neither penetrated the foam nor produced any significant
The pH value (typically 5) of the APP can be adjusted to a foam deformation, thereby maintaining the original structure.
neutral pH by applying different coatings. The pH-adjusted In addition, intumescent foams with ceramifying agents
APPs offer a greater compatibility to certain resins. Also the show better thermal insulation than those without agents or
viscosity stability of intumescent paints during storage less effective salts. As can be seen in Figure 5, the
should be more constant and not change dramatically, as is intumescent coatings with the ceramifying agents 1 and 5
the case with some lower quality APP types. The hydrophilic reach the critical temperature (500°C) eight minutes later
or hydrophobic properties of the APP can be adjusted by than the intumescent system without any additive. A
changing the surface polarity of the particles. Such products fire-resistance test carried out by an official testing
can be used in either solvent- or water-based paint systems. laboratory was applied to this system, and resulted in a
In general, coated APP particles are more compatible with glassy and hard structure without any cracking and flaking of
the matrix in which they are used. the protective coating. Thus, further optimisation of
intumescent coatings using ceramifying agents will lead to
Ceramifying agents improve the foam consistency new and improved steel protection systems with better fire
Ceramifying agents are an interesting and promising performance.
technology to improve the consistency of intumescent foam.
The use of selected ceramifying agents will increase the Results at a glance
strength and the resistance of the intumescent foam and at - Ammonium polyphosphates (APP) are playing an
the same time the adherence to the steel profile. important role in as flame-retardant additive in intumescent
Various additives have been tested in a traditional paints for the fire protection of structural steel.
intumescent system used in reactive systems for steel - Coated grades of APP significantly improve the coatings'
profile protection. The basic formulation of the intumescent performance: Formulations based on these grades show
coating contains three parts of APP II ("FR CROS 484"), better moisture resistance, higher thermal stability and more
one part of melamine and one part of pentaerythritol uniform intumescence layers, leading to better thermal
(compare formulations above). The basic formulation used insulation.
was: - The use of specific ceramifying agents in the formulations
APP II 35.7% greatly improves the consistency, i.e. the mechanical
melamine 11.9% stability, of the intumescent foams, adding to their fire
pentaerythritol 11.9% protection performance.

Vincentz Network +++ Schiffgraben 43 +++ D-30175 Hannover +++ Tel.:+49(511)9910-000

 Quelle/Publication: European Coatings Journal
Ausgabe/Issue: 10/2006
Seite/Page: 30

The authors:
-> Dr. Thomas Futterer is research and development
manager for flame retardants at Chemische Fabrik
Budenheim. He received his PhD in 1997 from the
University of Regensburg and joined Budenheim in 1999.
-> Dr. Hans Dieter Nägerl is vice president at Chemische
Fabrik Budenheim. He received his PhD in 1970 from the
University of Würzburg, Germany and joined Budenheim in
1986.
-> Vicens Mans is general manager of Budenheim Iberica.
He received his diploma of Industrial Chemistry from the
Engineering School of Barcelona in 1976. He is member of
the CEN-TC 127 and EAPFP, representing Spain.
-> Eduardo Tortosa is technical manager for flame
retardants at Budenheim Iberica. He received his Diploma
Degree in Chemistry in 1963 at the Chemical Institute of
Sarria (IQS). He joined Budenheim Iberica in 1996.
-> David Garcia is technical manager and qualitiy manager
for flame retardants at Budenheim Iberica. He received his
Diploma Degree in Chemistry in 1996 from the University of
Zaragoza, Spain. He joined Budenheim Iberica in 1999.
This paper was presented at the European Coatings
Conference "Fire Retardant Coatings", Berlin, 14/15
September 2007

Vincentz Network +++ Schiffgraben 43 +++ D-30175 Hannover +++ Tel.:+49(511)9910-000

 Quelle/Publication: European Coatings Journal
Ausgabe/Issue: 10/2006
Seite/Page: 30

Figure 1: General formula of APP with chain length n.

Vincentz Network +++ Schiffgraben 43 +++ D-30175 Hannover +++ Tel.:+49(511)9910-000

 Quelle/Publication: European Coatings Journal
Ausgabe/Issue: 10/2006
Seite/Page: 30

Figure 2: Improvement of the solubility of APP grades by different coating technologies

.

Vincentz Network +++ Schiffgraben 43 +++ D-30175 Hannover +++ Tel.:+49(511)9910-000

 Quelle/Publication: European Coatings Journal
Ausgabe/Issue: 10/2006
Seite/Page: 30

Figure 3 a-b: Moisture resistance of intumescent paints with different APP grades after
artificial weathering. a) water based paints A-C, b) solvent based paints D-F .

Vincentz Network +++ Schiffgraben 43 +++ D-30175 Hannover +++ Tel.:+49(511)9910-000

 Quelle/Publication: European Coatings Journal
Ausgabe/Issue: 10/2006
Seite/Page: 30

Figure 4: Visual observation of ceramifying effect. Left: sample with ceramifying

additive (salt 1: hard intumescence). Right: sample without additive (soft intumescence)
.

Vincentz Network +++ Schiffgraben 43 +++ D-30175 Hannover +++ Tel.:+49(511)9910-000

 Quelle/Publication: European Coatings Journal
Ausgabe/Issue: 10/2006
Seite/Page: 30

Figure 5: Temperature vs time curves of standard paints without ceramifying additives

and with ceramifying additives (salts 1, 3 and 5).

Vincentz Network +++ Schiffgraben 43 +++ D-30175 Hannover +++ Tel.:+49(511)9910-000

 Quelle/Publication: European Coatings Journal
Ausgabe/Issue: 10/2006
Seite/Page: 30

Vincentz Network +++ Schiffgraben 43 +++ D-30175 Hannover +++ Tel.:+49(511)9910-000

 Quelle/Publication: European Coatings Journal
Ausgabe/Issue: 10/2006
Seite/Page: 30

Vincentz Network +++ Schiffgraben 43 +++ D-30175 Hannover +++ Tel.:+49(511)9910-000

 Quelle/Publication: European Coatings Journal
Ausgabe/Issue: 10/2006
Seite/Page: 30

Vincentz Network +++ Schiffgraben 43 +++ D-30175 Hannover +++ Tel.:+49(511)9910-000