Construction and Building Materials 37 (2012) 190196

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Construction and Building Materials

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Characterisation of polymer concrete with epoxy polyurethane acryl matrix

Leon Agavriloaie a, Stefan Oprea b, Marinela Barbuta c,, Florentina Luca a
a

National Institute for Research and Development in Construction, Urban Planning and Sustainable Spatial Development URBAN-INCERC, Branch Iasi, 37, Prof. Anton Sesan, Iasi 700048, Romania b Petru Poni Institute of Macromolecular Chemistry Iasi, 41A, Grigore Ghica Voda, Iasi 700487, Romania c Gheorghe Asachi Technical University of Iasi, Faculty of Civil Engineering and Services, B-dul Prof.Dr.Doc. Dimitrie Mangeron 43, Iasi 700050, Romania

h i g h l i g h t s
" Polymer concrete was obtained from resin type epoxy polyurethane acryl and aggregates. " EPUAC is lightweight composite, with a high thermal and durability performances. " Mechanical properties of EPUAC are comparable with that of polyester concrete.

a r t i c l e

i n f o

a b s t r a c t
This paper studies a new type of polymer concrete obtained using epoxy polyurethane acryl and aggregates. Mechanical properties, such as: compressive strength, exural strength, elasticity modulus, pullout stress and adherence stress between cement concrete and polymer concrete were experimentally determined. Thermo-physical properties, such as: bulk density in natural and dry state, relative and absolute mass humidity, thermal conductivity, linear thermal dilatation, thermal shock strength, chemical resistance, frost-thaw resistance and water adsorption resistance were studied to establish the durability properties of the epoxy polyurethane acryl concrete. The experimental results have shown that epoxy polyurethane acryl concrete is a high performance, lightweight concrete with properties that recommend it as a possible replacement material for classical building materials. 2012 Elsevier Ltd. All rights reserved.

Article history: Received 20 May 2011 Received in revised form 25 June 2012 Accepted 22 July 2012 Available online 30 August 2012 Keywords: Epoxy polyurethane acryl Mechanical properties Polymer concrete Thermo-physical properties

1. Introduction Polymer concrete is a relatively new high performance material, which has widespread applications due to its advantages in comparison with cement concrete [16]. Among the advantages offered by polymer concretes are: excellent mechanical strength, fast curing time, very good adhesion properties, resistance to abrasion and weathering, waterproofness and good sound and thermal insulation properties [713]. There are numerous domains for the use of polymer concrete, such as the production of precast members; in hydraulic structures, such as dams, dikes, reservoirs and piers; highway surfaces and bridge decks; as well as in the petrochemical industry, underground constructions, road surfaces and coating or repairs materials in the chemical and food industry [2,10,14]. In preparing mortars or concretes, different types of polymers are used, such as polyester, epoxy, furan, vinyl, rubber, phenol and acrylic resins [1517]. Laws limiting styrene emissions
Corresponding author. Tel.: +40 232272859.
E-mail address: barbuta31bmc@yahoo.com (M. Barbuta). 0950-0618/$ - see front matter 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.conbuildmat.2012.07.037

will inuence the developments in unsaturated polyesters [15]. High strength epoxy resin-based polymer concretes have the biggest cost and are used in limited domains. New types of polymer developed for the concrete industry are intended to optimise the ratio of cost and performance [18,19]. Epoxy-urethane acryl [20 23] is an important polymer with improved properties: high strength to abrasion, exibility, elasticity, adsorption of shocks and good resistance in the environment. Polyurethanes have the advantage of low viscosity, good matrix bonding, a small reaction time and low cost. Polyurethane acryl adds the optical and durability properties of poly-acryl to polyurethane. The oligomer epoxy polyurethane acryl is 100% reactive and does not require solvent evaporation or special equipment for the recovery of solvent and thus, environment pollution and impact on the workers are minimised. The use of polyurethane acryl in the building material industry contributes in providing new advanced composites. The objective of this study is to establish the performance of a new polymer composite using epoxy-polyurethane acryl and aggregate, in order to determine its applicability as a building material.

L. Agavriloaie et al. / Construction and Building Materials 37 (2012) 190196 2. Experimental program 2.1. Materials 2.1.1. Polymer The polymer type epoxy polyurethane acryl and the hardener were obtained from the laboratory of Petru Poni Chemical Research Institute from Iasi, the methods of preparation are given in authors articles and are not presented in this paper [2025]. For preparing epoxy polyurethane acryl concrete (EPUAC), a quantity of 70% aggregates and 30% polymer are necessary for the homogeneity of mix and workability. Previous studies on polyester resin concrete using the same type of aggregates established this mix [26]. 2.1.2. Aggregate The aggregate type was crushed granite from a quarry having a density of 2400 kg/m3. In the mixture, the proportion of aggregates was 70% in equal dosages of two sorts: 01 mm and 13 mm. 2.2. Preparation of polymer concrete The samples were prepared in two stages: rst, the two sorts of aggregates were mixed, following which the aggregate mix was placed into moulds and the moulds lled with resin. A vibration table realised the compaction of the mixes. Different types of samples were used for testing according to the standards. After pouring, the samples of EPUAC were kept for 21 days until testing. 2.3. Experimental tests 2.3.1. Mechanical tests  Compressive strength. Five 70 mm sized cubes were tested in axial compression according to SR EN 12390-3:2002 [27].  Flexural strength. The tests were performed according to SR EN 12390-5:2002 [28], Fig. 1 on ve prisms of 70 70 210 mm.  Elasticity modulus. For determining the elasticity modulus, three samples of 25 25 80 mm were used (according to STAS 5585-71 [29]). The computational equation is:

191

load mid-span and tested in exure. The cross section had the dimensions: width b = 70 mm and depth h = 60 mm. The failure is produced at the contact zone between the cement concrete and polyurethane acryl concrete. 2.3.2. Thermo-physical tests  Bulk density in natural and dry state. The tests were done according to SR EN 7713:2004 [31] and SR EN 772-13:2001 [32] on ve samples with dimensions: L = 244.4246.4 mm; l = 244.8245.6 mm; d = 34.935.9 mm.  Relative and absolute mass humidity. For testing according to SR EN 771-3:2004 [31], SR EN 772-10:2001 [32], ve samples of the same size as in the case of density test were used.  Thermal conductivity. The test was done according to STAS 5912-89 [34] using the method of one sample body. The samples had the same sizes as in the case of density test. According to standard, the sample was maintained at a temperature of 105 C until constant mass. After that, the sample was introduced to a conductivity-device, equipped with measuring sensors that determine the thermal ux density, which crosses the sample from the top to the bottom in the central zone.  Linear thermal dilatation. The experimental tests were done according to SR EN ISO 10545-8:2000 [35] on six samples with dimensions: L = 61.564.0 mm; b h = 10 10 mm. The samples were dried at a constant temperature (110 5 C) until constant mass and then were introduced to a desiccator for cooling at ambient temperature. The initial length of the sample was measured and again at each temperature interval of 15 C. The heating rate was 5 1 C/ min. The coefcient of linear thermal dilatation al was calculated according to the relation:

al 1=L 0xDL=Dt

where L is the sample length at ambient temperature, mm; DL is the increase in length of sample between ambient temperature and 100 C mm; and Dt is the increase of temperature, C.  Thermal shock strength. The test was done according to SR EN ISO 10545-9:2000 [36] using the method of immersion. Five samples were used having the dimensions: L = 11.9512.00 mm; l = 3.323.52; h = 10 mm.  Chemical resistance. The tests were done according to SR EN ISO 10545-13:2001 [37] on ve prismatic samples, having an initial mass between: 26.716 and 45.842 g, Fig. 4. For the tests the following solutions were used: (a) (b) (c) (d) Solution Solution Solution Solution of of of of hydrochloric acid 3% (volumetric percentage). hydrochloric acid 18% (volumetric percentage). potassium hydroxide (KOH), 30 g/L. potassium hydroxide (KOH), 100 g/L.

E Dr =De N =mm2

 Maximum pull-out stress for a plain bar, U = 16 mm. The tests were realised according to STAS 5511-1989 [30]. Three 70 mm cubic samples were tested, (Fig. 2ac).  The adherence stress between cement concrete and polyurethane acryl concrete. The tests were done according to a method conceived by the Research Institute in Construction INCD URBAN INCERC from IasiRomania, on three samples, Fig. 3ad; the samples were simply supported and loaded with a concentrated

The samples were immersed in the solutions and kept in the laboratory for 12 days at a temperature of 20 2, Fig. 4. After that, the samples were exposed to stream for 5 days and were then boiled for 30 min. Following this, the samples were recovered, wiped and dried to a constant mass in an oven at 110 C. Once dry, the samples were weighed and the loss of mass Dm, was determined. This then allowed the determination of the chemical resistance class- CRC-according to SR EN ISO 10545-13:2001 [37].  Frost-thaw resistance. The tests were done according to SR EN ISO 772-18:2003 [38] on nine samples with dimensions: L = 3438 mm; l = 3234; h = 33 36 mm.  Water adsorption. The tests were carried out according to SR EN ISO 105453:1999 [39] on three prismatic samples with an initial mass between: 124.123 and 137.552 g. The water adsorption of the samples by boiling in water at 100 C for 2 h and then cooling in water for a further 2 h and 15 min was a hardness test for EPUAC.  Microstructure of polymer concrete. A scanning electron microscope (SEM) Vega Tescan analysis running at 30 kV and selenium detectors were used to investigate the particles morphology. An Ag sputter coating on the surface of the specimens provided a greater depth of image.

3. Results and discussion The mechanical and thermo-physical properties determined on EPUAC are presented in the following tables. For a better characterisation of EPUAC, the results were compared with the experimental data obtained in previous studies on polyester concrete (PEC) [26], which has a similar composition to EPUAC.

Fig. 1. Polyurethane acryl concrete sample tested in exure.

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Fig. 2. Pull-out test: (a) pouring of samples; (b) test sample; and (c) tested sample.

3.1. Mechanical tests Table 1 presents the experimental values of the mechanical characteristics of EPUAC. The average value of compressive strength is fc,cube = 52.5 N/mm2, which can be considered to be a high value for this type of microconcrete. The average value of exural strength is fcf = 11.52 N/mm2. Comparing the results with polyester resin concrete (PEC), the following observation can be stated:  the compressive strength of EPUAC is smaller than the minimum value of PEC, which was fc,cube = 67.1 N/mm2, at 27 days;  the exural strength was bigger than the minimum value of PEC, which was fcf = 10.54 N/mm2. The experimental value for elasticity modulus is given in Table 1: Ebmed = 2434 N/mm2. This value is smaller than that of Portland cement concrete, which has an elasticity modulus of 3500 N/mm2

(SREN 1992/2006 [40]) but which has the same compressive cube strength. The adherence characteristics have shown a good bond between EPUAC and steel (the maximum pull-out stress for a plain bar is: smax = 2.89 N/mm2) and also a good adhesion between EPUAC and cement concrete (the adherence stress was smax = 4.7 N/ mm2). These values are smaller than in the case of PEC, for which minimum values were 3.52 N/mm2 and 5.6 N/mm2, respectively.

3.2. Thermo-physical tests Table 2 presents the experimental values of the thermo-physical properties of EPUAC. The values of bulk density in the dry and natural states of EPUAC are smaller than in the case of PEC, which were qnat = 1936 kg/m3 and qdry = 1954 kg/m3. The experimental density of epoxy polyurethane acryl concrete characterises it as lightweight concrete.

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Fig. 3. Adherence test: (a) samples for adherence tests; (b) testing in exure; (c) left view; and (d) right view.

Absolute mass humidity was: Uabs = 1.23%. Relative mass humidity was: Urel = 1.21%. For PEC, the absolute mass humidity had the value 0.07%.  Thermal conductivity. The result that is the average of ve samples is given in Table 2. The thermal conductivity at 0 C was: k0 = 0.425 W/m K, smaller than that of PEC, for which k0 = 0.49 W/m K. The EPUAC presented thermal insulation properties superior to PEC.
Fig. 4. Samples tested to corrosion: E 7.2 in 3% HCl solution; E 7.3 in 18% HCl solution; E 7.4. in 30 g/L KOH solution; E 7.5 in 100 g/L KOH solution.

From all thermal characteristics, EPUAC has a thermal conductivity smaller than that of PEC, which indicates a better behaviour for thermal isolation. All other properties were near those values obtained for PEC. The results for relative and absolute mass humidity are presented in Table 2:

 Linear thermal dilatation. The experimental result is given in Table 2. The average value of linear thermal dilatation on six samples of epoxy-polyurethane concrete was: am = 56.03 106 K1 (for ordinary concrete the coefcient of thermal dilatation varies between 4 106 and 14 106 K1 (SREN 1992/ 2006 [40]).  Thermal shock strength. The average value of water absorption was: Abmed = 0.0108% (Table 2). Defects after testing: from visual examination at 30 cm distance and with illumination of

194 Table 1 Mechanical properties of EPUAC. Mix EPUAC Compressive strength, fc,cub (N/mm2) 52.5

L. Agavriloaie et al. / Construction and Building Materials 37 (2012) 190196

Flexural strength, fcf, (N/mm2) 11.52

Elasticity modulus in compression, Ebmed (N/mm2) 2434

Maximum pull-out stress, smax (N/mm2) 2.89

Adherence stress, sad (N/mm2) 4.7

Table 2 Thermal properties of EPUAC. Properties Density Natural state, qnat Density Dry state, qdry Mass humidity Relative, Urel Mass humidity absolute Uabs Thermal conductivity at 0 C, k0 Linear thermal dilatation, am Thermal shock strength, Abmed Water adsorption, Wi Loss of compressive strength after 50 frost-thaw cycles UM kg/m3 kg/m3 % % W/ mK C 1 % % % Value 1857 1834 1.21 1.23 0.425 56.03 106 0.0108 0.627 11.58 Fig. 5. Samples after frostthaw cycles tested in compression.

300 lx on a surface treated with methyl blue, it was observed the samples did not present modications, such as: deformations, swelling, cracks, exfoliations or material dislocations. From this point of view, this new polyurethane acryl concrete has a very good behaviour to extreme climatic temperature. Chemical resistance. The tests for the action of chemical aggressive agents (HCl and KOH solutions) have established that EPUAC has a good chemical resistance (Table 3). In all cases, there were no defects on the polymer concrete samples, according to SR EN ISO 10545-13:2001. Water adsorption. Water adsorption by the boiling method for polymer concrete had the average value: Wi = 0.627% (Table 2). It can be appreciated that EPUAC behaved well in this physical test, in view of the fact that for PEC, the water absorption was 0.49% and for cement concrete, it was over 1.0% [26]. Frost-thaw resistance. After 50 frost-thaw cycles in the temperature range: 15 C to +20 C, the polymer concrete with epoxy polyurethane acryl had a loss of compressive strength, fc, of 11.58%. However, before the testing in compression, the samples were analysed by the naked eye and by 10 magnication and there did not appear to be any swelling, cracks, exfoliations or material dislocations (Table 2, Fig. 5). According to the Romanian standards, after 50 frost-thaw cycles, the reduction of strength must be smaller than 25% and EPUAC accomplished this condition. Microstructure of polymer concrete. Fig. 6a shows the surface of polymer concrete made using epoxy-urethane acryl and aggregates at 500 magnication. The picture clearly shows the

presence of voids having maximal diameters of about 0.35 mm in the polymer concrete. The resin is homogeneous in the mass and covers the aggregates but in some places the polymer is agglomerated, as can be seen in Fig. 6b. 4. Conclusions The aim of the present research focused on a new type of polymer concrete, EPUAC, having in mind the possibility of its use as a construction material. Polymer concrete was obtained from resin type epoxy polyurethane acryl with two sorts of aggregate: 01 mm and 13 mm. Two types of tests were done for characterising the properties of this new material: mechanical tests and thermo-physical tests. Compressive strength, exural strength, elasticity modulus, pull-out stress and adherence stress between cement concrete and polymer concrete characterised EPUAC as a material of high quality with mechanical properties comparable with that of polyester resin concrete. Thermo-physical tests (bulk density in natural and dry states, relative and absolute mass humidity, thermal conductivity, linear thermal dilatation and water adsorption) have revealed a lightweight composite with a high thermal and durability performance. The durability tests revealed a good resistance of EPUAC when subjected to thermal shock, chemical aggression or frost-thaw cycles. Thermal insulation properties of EPUAC are superior to those of classical cement concrete or PEC, leading to the enhancement of thermal comfort, simultaneously with energy cost savings.

Table 3 Determination of chemical resistance. No. 1 2 3 4 5 Initial mass 31.029 31.346 26.716 45.842 30.990 Mass before testing 30.817 31.160 26.589 45.632 30.849 Mass after testing 31.016 26.417 45.400 30.529 Difference (loss) of mass after testing 0.144 0.172 0.232 0.320 Difference of mass after testing 0.464 0.651 0.511 1.048 Class of chemical resistance ULA UHA ULA UHA Observations Witness sample that is not tested Sample in 3% HCl solution Sample in 18% HCl solution Sample in KOH 30 g/L solution Sample in KOH 100 g/L solution

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Fig. 6. Scanning electronic microscopy for polymer concrete samples with epoxyurethane acryl and aggregate (symbolised EPUAC).

Through use of a scanning electron microscope, the microstructure of EPUAC was studied. The microstructure is homogeneous and the voids are small in diameter and uniformly distributed, contributing to porous structure, favourable for thermal conductivity. The good durability properties near the high mechanical properties of EPUAC, have shown that this concrete is a high performance lightweight concrete. Some further additions to the composition of EPUAC can result in an improvement of its properties but this must be tested experimentally. The experimental results presented are only for the new basic mixture of epoxy polyurethane acryl and aggregates. This type of polymer concrete (EPUAC) having high mechanical and durability properties, can be used in different construction domains, such as: industrial buildings where chemical and thermal protection is required, or as insulation or waterproong material, for realising oors subject to shocks or chemical agents, for structural consolidation and for realising high structures. Acknowledgement This research was funded by a grant from ANCS Romania, no 14 N/2010.

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[37] SR EN ISO 10545-13:2001. Ceramic tiles. Part 13: Determination of chemical resistance. [38] SR EN 77218:2003. Methods of test for masonry units. Part 18: Determination of freeze-thaw resistance of calcium silicate masonry units.