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Procedia Engineering 117 (2015) 119 – 125

International Scientific Conference Urban Civil Engineering and Municipal Facilities,

SPbUCEMF-2015

Estimation of the Pores Dimensions of Intumescent Coatings for

Increase the Fire Resistance of Building Structures
Marina Gravita, Vasiliy Gumenyuka, Maxim Sychovc, Oleg Nedryshkina, *
a
St. Petersburg State Polytechnical University, Politekhnicheskaya, 29, Saint-Petersburg, 195251, Russia
c
Saint-Petersburg State Institute of Technology (Technical University), 26, Moskovsky pr., Sain-Petersburg, 190013, Russia.

Abstract

The authors first examined the possibility of estimating the pore space coating of intumescent coatings for increase the fire
resistance of building structures using the program “Video tests”.
© 2015
© 2015Published
The Authors. Published
by Elsevier byisElsevier
Ltd. This Ltd. article under the CC BY-NC-ND license
an open access
Peer-review under responsibility of the organizing committee of SPbUCEMF-2015.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of SPbUCEMF-2015
Keywords: Fire resistance, intumescent coatings, pore space, foam, height of foam, shape, dimension

1. Introduction

Polymer composites are widely used as materials featuring unique properties determined by an adjustable
combination of different materials with complementary properties and suitable for application using inexpensive
high throughput technologies like brush painting and spray coating [1 – 7]. Particularly, intumescent coatings are
used to increase the fire resistance of various buildings [8 – 16].
In addition to the characteristics and concentrations of individual components, an important factor responsible
for the properties of composites is their structure. In our previous research it was shown that control of composite
structure allowed improving fire resisting property and mechanical properties of composites and coatings
significantly [1 – 16].
Thus, it was reasonable to expect that the structure of composite should influence the properties of fire protecting

* Corresponding author. Tel./fax: +7 (812) 712-7791

E-mail address:dnedryshkin@gmail.com

1877-7058 © 2015 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of SPbUCEMF-2015
doi:10.1016/j.proeng.2015.08.132
120 Marina Gravit et al. / Procedia Engineering 117 (2015) 119 – 125

intumescent composites and coatings. Such influence has been studied and presented in this paper.
When exposed to temperatures of above 150°C intumescent coatings form the foam – solid and breakable porous
composite substance with low thermal conductivity in which the pores are formed by the fixation of gases in the
hydrocarbon backbone that were formed during thermal decomposition [8 – 16]. Due to the formation of the foam
the thickness of the coating increases substantially.
The expansion factor of such coatings K is then defined as the ratio of the thickness of the expanded layer h to
the thickness of the original film h0 [17]:

‫݄ = ܭ‬/݄଴ (1)

Depending on the size and location of the pores in the foam its thermal conductivity will change and,
accordingly, the parameters of the fire retardant efficiency of the intumescent coating will also change. Fire-
retardant efficiency is defined as the time necessary for a steel construction coated with the tested fire retardant
coating to reach the critical temperature (500 °C) [18].
For the European Community countries the usage of fire protection (including intumescent coatings and
composites) is regulated by the European norms and technical requirements [19 – 26], and for each type of substrate
(material) and construction the corresponding normative document is applied [16, 21 – 28]. To get the required
efficiency parameters of the flame-retardant coating the resulting foam should be evenly distributed on the surface
of the test sample and have an optimal multiplicity of swelling (optimal expansion factor). The pores of the formed
foam should be of the optimal size, preferably of closed type, of spherical shape and should be evenly distributed in
the volume [14, 15, 29].
In this paper the evaluation of the foam pores was carried out for the first time by measuring the plane parameters
of cuts and then calculating the stereological parameters of the structure (the parameters of the spatial structure of
three-dimensional objects calculated with the help of their two-dimensional images) using the "VideoTest" software
[30].
This software allows one to measure the thickness, study the fractures, and perform a phase analysis of the
coatings, as well as to evaluate the pore space of materials. The software can be used to analyse the pictures of
porosity of polished and transparent sections, as well as macro-objects.

2. Experimental

Paints were based on acrylic styrene resins and melamine-formaldehyde resins, because these coatings have a
high expansion factor.
Paints for coatings were fabricated as follows: the components were mixed by means of a basket mill. Then the
paints were coated onto primed carbon steel substrates with a brush with the thickness of 1 mm.
After that the samples were put into an electric oven for 5 minutes to obtain the foams. The foams were obtained
at 500 °C, since the maximum height of its layer is achieved at this temperature, and the pores are well
differentiated. According to [17], the temperature of 600 °C is not feasible for research, because the foam is nearly
completely burned out. Whereas 500 °C is adopted as the critical temperature in the standard for fire-retardant
efficiency [18], which is declared in the main sections of the authentic European standard [31].
Further images of the foam cross-sections were studied. The main provisions of the methodology are as follows
[30]:
The method is based on counting the number of objects of various classes on an image and calculating their
percentage.
The method can be used for either powder or solid materials whose structure is formed from components of
various types differing in geometrical or optical parameters.
How the method works:
- objects of all types are detected by brightness or colour automatically on the captured image;
- if necessary, some additional preparations for the measurements are made: removing small extraneous details
from the image, edges smoothing, filling holes, automatic separation of contacting objects;
 Marina Gravit et al. / Procedia Engineering 117 (2015) 119 – 125 121

- after measuring the objects their classification is performed. Objects are assigned to one class or another with
the help of the classifiers the program contains. Operators specify the parameters and their numeric bounds
themselvesor "teach" the classifier pointing out the class an object refers to on the image;
- in accordance with the measurement results the classification percentages between the classes are calculated,
the results can be presented as a table or a bar chart.
Images processed with the help of this procedure along with the results of the percentage calculation can be saved
in a single document or a database (Fig. 1).
The effect of the foam formation, the achievement of the optimal expansion factor, the size and shape of the
pores depend on the composition of the intumescent system. In this study, the following composition is selected:
ammonium polyphosphate, melamine/chlorinated paraffin wax, pentaerythritol. The optimum content of the
components was selected with the method of thermogravimetric analysis based on the average volume of the coke
residue, as well as after obtaining satisfactory performance parameters (adhesion, impact strength, sedimentation
stability) [13, 14].

Fig. 1. The pictures of pore size distribution, statistics and tables with stereological parameters in the "Video Test" program interface

3. Results and discussion

Pictures of the foams in cross-sectional view for some coatings and received histograms of pore size distributions
are shown in Fig. 2 – 6.

Fig. 2. Foam of the coating based on the melamine-formaldehyde resin (k-1) and the histogram of its distribution of the pores (K = 87)
122 Marina Gravit et al. / Procedia Engineering 117 (2015) 119 – 125

Fig. 3. Foam of the coating based on the melamine-formaldehyde resin (k-2) and the histogram of its distribution of the pores (K = 80)

The intumescent coatings based on the melamine-formaldehyde resin k-1, k-2 and k-3 (Fig. 2 –4) contain
ammonium polyphosphate (20 – 30%), pentaerythritol (8 – 10%), melamine (8 – 10%). The average ratio in the
intumescent system is represented as 30:10:10 – ammonium polyphosphate: melamine: pentaerythritol. The coating
k-2 also contains chlorinated paraffin wax (4%).

Fig. 4. Foam of the coating based on the melamine-formaldehyde resin (k-3) and the histogram of its distribution of the pores (K = 84)

The coatings based on the acrylic styrene resins (the average ratio in the intumescent system is also represented
as 30:10:10) do not have such high values of K as the melamine resin, however, for the coating a-4 containing 5.7%
of chlorinated paraffin the foam has the structure of large and irregular pores, resulting in intensive gas formation
(Fig. 5). The small pores in the dense foam of sample a-5 (ammonium polyphosphate, pentaerythritol, melamine =
30:15:15) with a wide size distribution (Fig. 6) make it possible to forecast the stability of the foam when tested on
the parameters of fire-resistance rating in accordance with [18].
 Marina Gravit et al. / Procedia Engineering 117 (2015) 119 – 125 123

Fig. 5. Foam of the coating based on the acrylic styrene resins (a-4) and the histogram of its distribution of the pores (K = 70)

Further research was carried out in terms of searching for relationships between the size and distribution of the
pores of the coatings on the one hand, and mass loss in case of thermogravimetric analysis on the other in order to
forecast the parameters of the fireproof efficiency of the samples (a steel column with a flame retardant
coating)during standard fire test [18]. The test [18] was carried out without static load at four-sided thermal
exposure before limiting conditions were achieved by the test sample. As the limiting conditions we adopted the
achievement of the critical temperature (500 °C) of two steel prototypes (I-beams with the height of 1700 mm).
Thermocouple on the sample was set by caulking with an average cross section of the sample on the wall of an I-
beam and on the interior surfaces of the I-beam shelves. An nnprotected steel structure typically reaches a limit
temperature in 10 – 15 min.

Fig. 6. Foam of the coating based on the acrylic styrene resins (a-5) and the histogram of its distribution of the pores (K = 54)

As preliminary results based on the experimental data according to the fire tests [13, 14], it can be stated that in
order to ensure that a protected sample reaches 500 °C after more than 30 minutes of heating the pores in the foam
of the intumescent fire-retardant coatings based on melamine and acrylic resins should be distributed as follows: the
proportion of the pores with a diameter of 0.5 – 1 mm should not exceed 30% and those with a diameter of 2 mm –
3% of the total amount of the evenly distributed pores (Fig. 6).
At the same time the value of the expansion factor K for the intumescent coating should be in the range of 40 –
65, since at higher K values the foam formed on the test piece (steel column) cracks and delaminates.
As the data have shown [13 – 15], the loss of mass of the coating during thermogravimetric analysis should not
exceed 45% of the initial value during the increase of the temperature in the test chamber up to 500 °C [32], as if the
124 Marina Gravit et al. / Procedia Engineering 117 (2015) 119 – 125

weight loss is larger the foam decomposes and it is not retained on the support structure, as a result, it does not
ensure fire resistance of steel constructions.

4. Conclusions

Research in this direction continues, confirming the statement that one of the main factors influencing the
efficiency of fire-retardant intumescent coatings for steel building construction is the structure of the formed foam,
particularly the size, shape and the distribution of the formed pores.

References

[1] Myakin, S.V., Korsakov, V.G., Panova, T.I., Sosnov, E.A., Fomchenkova, Yu.C., Sychov, M.M., Shilova, O.A. Effect of the Modification of
Barium Titanate on the Permittivity of Its Composites with Cyanoethyl Ester of Polyvinyl Alcohol (2011) Glass Physics and Chemistry, 6, pp.
624 – 628.
[2] Sychov, M., Syrkov, A., Nakanishi, Y., Hara, K., Kominami, H., Mimura, H. Acid-base aspect of control of nanocomposite electrical
properties (2013) Smart Nanocomposites, 2, pp. 51 – 57.
[3] Alekseev, S.A., Sychev, M.M., Korsakov, V.G., Rodionov, A.G., Ezhenkova, L.L. The effect of composition and structure on dielectric
characteristics of films based on poly(vinyl alcohol) cyano ether (2009) Polymer Science, Series A., No. 9, pp. 1002 – 1007.
[4] Khamova, T.V., Kolovangina, E.S., Myakin, S.V., Sychov, M.M., Shilova, O.A. Modification of submicron barium titanate particles via sol-
gel synthesis of interface layers of SiO2 for fabrication of polymer-inorganic composites with improved dielectric properties (2013) Russian
Journal of General Chemistry, 83 (8), pp. 1594 – 1595.
[5] Cheremisina, O.A., Popov, V.V., Sirotinkin, N.V., Korsakov, V.G., Sychev, M.M. Conducting polymeric composites based on butadiene-
acrylonitrile latex (2010) Rus.J.App.Chem., 83(4), pp. 718 – 722.
[6] Myakin, S.V., Sychov M.M., Vasina E.S., Ivanova A.G., Zagrebel’nyi O.A., Tsvetkova I.N., Shilova O.A., Relationship between the
composition of functional groups on the surface of hybrid silicophosphate membranes and their proton conductivity (2014) Glass Physics and
Chemistry, Vol. 40, No. 1, pp. 97 – 98.
[7] Korsun, V., Vatin, N., Korsun, A., Nemova, D. Physical-mechanical properties of the modified fine-grained concrete subjected to thermal
effects up to 200°C (2014) Applied Mechanics and Materials, 633 – 634, pp. 1013 – 1017.
[8] .RVWLü59DWLQ10XUJXO9)LUH6DIHJXDUGVRI³3ODVWEDX´&RQVWUXFWLRQ$SSOLHG0HFKDQLFVDQG0DWHULDOV-726, pp. 138 –
145.
[9] Vatin, N., Gorshkov, A., Nemova, D., Staritscyna, A., Tarasova, D. The energy-efficient heat insulation thickness for systems of hinged
ventilated facades (2014) Advanced Materials Research, Vols. 941 – 944, pp. 905 – 920.
[10] Lazarevska, M., Cvetkovska, M., Knezevic, M., Trombeva Gavriloska, A., Milanovic, M., Murgul, V., Vatin, N. Neural network prognostic
model for predicting the fire resistance of eccentrically loaded RC columns (2014) Applied Mechanics and Materials, 627, pp. 276 – 282.
[11] Salminen, M., Heinisuo, M. Numerical analysis of thin steel plates loaded in shear at non-uniform elevated temperatures (2014) Journal of
Constructional Steel Research, 97, pp. 105-113.
[12] Salminen, M., Heinisuo, M. Shear buckling and resistance of thin-walled steel plate at non-uniform elevated temperatures (2011) 10th
International Conference on Steel Space and Composite Structures, pp. 267-276.
[13] Krasheninnikova, M.V. Flame retardants intumescent materials based on the organic films (2006) Lakokrasochnye materialy i ikh
primenenie [The Russian Coatings Journal] No. 12, pp. 2 – 4. (rus)
[14] Krasheninnikova, M.V. Povysheniye predelov ognestoykosti stalnykh stroitelnykh construktsiy ognezashchitnym vspuchivayushchimsya
pokrytiyem s povyshennoy atmosferostoykostyu. Avtoref. diss. kand. techn. nauk [Increasing the limit of fire resistance of steel constructions
fireproofing intumescent coating with high weatherability. Synopsis Dr. techn. sci. diss.] (2007) St. Petersburg. St-Petersburg University of
State Fire Service of EMERCOM of Russia Publ., 23 p. (rus)
[15] Gravit, M.V. Evaluation of pore space form of intumescent fire retardant coating (2013) Fire and Explosion Safety, No. 5, pp. 33 – 37.
[16] Eremina, T.Y. Gravit, M.V., Dmitrieva, Y.N. Means of fire protection of building structures. Analysis of the general provisions of the
Russian and European regulations (2012) Architecture and Construction of Russia, No. 8, pp. 24 – 29.
[17] State Standard of the Russian Federation 12.3.047-2012. Occupational safety standards system. Fire safety of technological processes.
General requirements. Methods of control. Moscow, Standartinform Publ., 1998, 84 p. (rus)
[18] State Standard of the Russian Federation 53295-2009. Fire retardant compositions for steel constructions. General requirement. Method for
determining fire retardant efficiency. Moscow, Standartinform Publ., 2009, 9 p. (rus)
[19] BS EN 13501-2:2007+A1:2009. Fire classification of construction products and building elements. Part 2: Classification using data from fire
resistance tests, excluding ventilation services [Electronic resource]. System requirements: Adobe Acrobat Reader, URL:
http://shop.bsigroup.com/ProductDetail/?pid=000000000030169566 (retrieved 03.04.2014).
[20] EOTA, "Guideline for European technical approval of fire protective products" – 2006, [Electronic resource]. System requirements: Adobe
Acrobat Reader, URL: http://www.eota.eu/en-GB/content/etags-used-as-ead/26/ (retrieved 25.11.2014).
[21] ENV 13381-3:2002. Test methods for determining the contribution to the fire resistance of structural members – Part 3: Applied protection
to concrete members [Electronic resource]. System requirements: Adobe Acrobat Reader, URL:
http://shop.bsigroup.com/ProductDetail/?pid=000000000030067949 (retrieved 12.02.2014).
 Marina Gravit et al. / Procedia Engineering 117 (2015) 119 – 125 125

[22] BS EN 13381-4:2013. Test methods for determining the contribution to the fire resistance of structural members – Part 4: Applied protection
to steel members [Electronic resource]. System requirements: Adobe Acrobat Reader, URL:
http://shop.bsigroup.com/ProductDetail/?pid=000000000030256847 (retrieved 12.02.2014).
[23] ENV 13381-5:2014.Test methods for determining the contribution to the fire resistance of structural members – Part 5: Applied protection to
concrete/profiled sheet steel composite members [Electronic resource]. System requirements: Adobe Acrobat Reader, URL:
http://shop.bsigroup.com/ProductDetail/?pid=000000000030254409 (retrieved 12.02.2014).
[24] EN 13381-6:2008. Test methods for determining the contribution to the fire resistance of structural members. Part 6. Applied protection to
concrete filled hollow steel columns [Electronic resource]. System requirements: Adobe Acrobat Reader, URL: https://shop.austrian-
standards.at/Preview.action;jsessionid=87F0CF23C65FAF2FDFE4533BBDEAE970?preview= &dokkey=316998&selectedLocale=en
(retrieved 12.02.2014).
[25] ENV 13381-7:2002 Test methods for determining the contribution to the fire resistance of structural members – Part 7: Applied protection to
timber members [Electronic resource]. System requirements: Adobe Acrobat Reader, URL:
http://shop.bsigroup.com/ProductDetail/?pid=000000000030067954 (retrieved 12.02.2014).
[26] EN 13381-8:2013 Test methods for determining the contribution to the fire resistance of structural members – Part 8: Applied protection
[Electronic resource]. System requirements: Adobe Acrobat Reader, URL:
http://shop.bsigroup.com/ProductDetail/?pid=000000000030256862 (retrieved 12.02.2014).
[27] Gravit, M.V. Regulatory documents of the European Community, which establish requirements for conformity assessment fireproof
intumescent coatings for building construction (2013) Lakokrasochnye materialy i ikh primenenie [The Russian Coatings Journal] No. 3, pp.
38 – 43. (rus)
[28] Gravit, M.V. Harmonization of Russian and European regulatory documents establishing the methods of fire tests of building structures with
the use of fire protection (2014) Fire and Explosion Safety, No. 5, pp. 38 – 44.
[29] Bahmetyev, V. V., Sychev, M. M., Krasheninnikova, M. V. Opyt prakticheskogo ispolzovaniya programmy "VideoTesT" na kafedre
teoreticheskikh osnov materialovedeniya SPGTI(TU) [Practical experience in the use of the program "Video Test" at the department of
theoretical bases of Materials SPbSTI (TU)] (2008) Sbornik tezisov 4 prakticheskogo seminara "Sovremennyye tekhnologii v mettallografii"
[Proc. 4 Int. Symp. "Modern technologies in metallography "] St. Petersburg, p. 234. (rus)
[30] Website of the Company VideoTesT [Electronic resource]. System requirements: Adobe Acrobat Reader, URL: http://www.videotest.ru/
(retrieved 07.01.2015).
[31] EN 1363-1:1999. Fire resistance tests. General requirements. Published: 15 November 1999 [Electronic resource]. System requirements:
Adobe Acrobat Reader, URL: http://shop.bsigroup.com/en/ProductDetail/?pid=000000000019969914 (retrieved 12.02.2014).
[32] National State Standard of the Russian Federation 53293-2009. Fire hazard of substances and materials. Materials, substance and fire
protective means. Identification by thermal analisyis methods (2011) Standartinform Publ., 23 p. (rus)