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Boyka Doychinova Nikolova Belcheva
Institute of Soil Science, Sofia, Bulgaria email:

ABSTRACT In a model experiment it was established that the addition of water-soluble thermo-reactive resin containing epoxy and phenol-formaldehyde composite to the concrete mixture improves its frost and corrosion resistance; decreases water absorption and permeability, which results in increasing the exploitation durability of the hydro- equipments constructed with the purposes and for the conditions of the irrigation agriculture. Key words: Hydro-technical, Polymer composite, Concrete- polymers.

INTRODUCTION Creating of new recipes about complex concrete composites with use in the hydro-technical and hydro-ameliorative constructions is an effective engineering approach and solution for the purposes and conditions of irrigation agriculture in our country. Through well quantified introduction of suitable polymer additives is received a concrete- polymer product , respectively a cement-polymer and they have a proper application in accordance with the determined geophysical and geochemical conditions, and also in compliance with the project parameters of the hydro- equipment and the quality characteristic of transported by it irrigation water. The orientation is to use water soluble thermo- reactive resins: epoxy and phenol- formaldehyde. In this manuscript are reflected some results from series of investigations on basic indexes about hydro-concrete polymers with use in the irrigation agriculture. Bulgarian produce of complex resins were studied. The chemical reactions of their production are discussed in details.

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According the practical, applicable conditions, compared with the results from the laboratory model experiment was chosen the recipe of the composition. As a significant moment, however, has to be accentuated on proving of the possibilities about the use of phenol-formaldehyde resin as a type of polymer additive. For this purpose was carried out a huge investigation work about optimization of the recipe composition in two directions: - Choice of thermo reactive resin modification; - Optimization of recipe composition: resin and hardener, with technological possibilities the resin to harden in the temperature interval of -15 C to 55 C in short technological time, at durable adhesion to a wet base; - Optimization of composition work: resin- hardener-filler and evaluation of the quality indexes. MATERIAL. INVESTIGATION . ANALYSIS Based on the results from the specialized laboratory research work, as well as in the natural conditions and considering the technique economical reasoning from the introduction of the new product according the project decision of the problem, additional investigations were carried out with the aim to establish the exploitation durability in years. By definition, as a base index at creation of the recipe compositions, is accepted the property degree of saturation, which necessitates the clarification of the following: The chemistry, physic-chemical properties and structure of the investigated polymer products (resins), which can determine 20-25% of the saturation degree in comparison with the participating in the total resin composition additional substances, such as cement plus hardener in the production of the polymercement with recommended application as working putty-mixture for local repair works on corroded surfaces. The chemistry, physic-chemical properties and structure of the investigated composition of cement plus filler plus water solution of the thermo-reactive polymer resin (TRPR) determine 40 to 50% of the saturation in the composition of the concrete mixture- cement : sand : gravel = 1 : 2 : 2 at water to cement ratio = 0.45, and at hardener/ TRPR = 0.05 (5% of hardener in the mixture). The received concrete-polymer successively is experimented at construction of hydro-equipments in zones with dangerous and unstable geophysical characte-

BALWOIS 2008-Ohrid, Republic of Macedonia-27, 31 May 2008


ristic; in hydro-equipments, constructed at very rough terrains; in hydroequipments with specific geometry of construction; in highway and main channels of fast flows; in transport of irrigation water with aggressive and corrosive characteristics, and so on. In the conditions of water deficit and continuous periods of drought in Bulgaria during the last years, as well as in the existing statues irrigation agriculture hydro-net it is exceptionally important and with need to limit urgently the loss of useful irrigation water through filtration. The use of concrete-polymers and cement-polymer composites is one possibility of durable solution of the upper stated problems. In this manuscript are suggested results from additional investigations on the porosity, water take up, corrosion resistance, water permeability and frost resistance of the hydro-equipments constructed from concrete-polymers. Corrosion resistance The model investigations are carried out in specialized laboratory on produced according the standard requirements for continuity of accumulation of toughness 28x24h under water, matrix samples with dimensions 16/4/4cm, deepen in water solutions with pH 6, 8, and 9, containing SO4-2, NO3-, CL-, , H+, OH-, Fe+2, Fe+3, CH3COO-, P+3, P+5, K+. The temperature cyclic loading of: -15C (5x24h) + 20C (5x24h) + 55C (5x24h) was recommended for the corrosion affecting factor temperature in accordance with the annual seasons. Frost resistance This index was investigated at the following technological regime: -15C x 10h in freezing camera, 20C x14h under water, outside the freezing camera for total of 100cycles, or 3 months time. pHH2O was 7.2. The results are shown in Table 2. Water take up and water saturation The index water take up is investigated on cubical matrix forms (15x15x15 cm). The aim is gradually for the time of absorption: 24h= 1/3 of the body deepen in water + 24h= 2/3 of the body deepen in water + 5x24h = stay of the whole body under water. The following results were received: -samples (TRPR addition) the water absorption mean= 0.98%; -control samples (without TRPR addition) the water absorption mean = 3.21%; The investigation results showed 3 times higher water absorption of the control samples as compared to those of the experimentally produced samples with TRPR addition.

BALWOIS 2008-Ohrid, Republic of Macedonia-27, 31 May 2008


The approach at determining of the property water saturation (Ws) was realized in experimental set up, in which was included a vacuum pump, with which was introduced a water flow through the experimental body to the visual determination the end of the process (lack of air bubbles in the water cork at the opposite side). The total number of the experimental bodies was six control and six samples. The following results were obtained: - Water saturation of samples was - Ws mean=1.42% - Water saturation of controls was- Ws mean = 4.01% The results of the investigation showed 2.79 times higher saturation at the control samples in comparison with that of the experimentally produced samples with TRPR addition. Capillary water take up To determine the capillary water take up (Wcw) were used prismatic matrix forms (5/5/2cm) at technological regime standard and test samples stay under water for 5x24h time. The following results were received: Test Samples - Wcw mean= 0.81% Standard samples- Wcw mean= 1.3% The results from the experiments showed, that the capillary water take up is 1.5 times higher than at the standard samples in comparison with that of the test samples, produced with TRPR addition. Water permeability To determine the water permeability (WP) of the concrete polymers were tested samples with cylindrical form d:h=70:20mm (diameter to height ratio= 70:20mm). The method of Stalkin - Solnceva - Popova - Natov - Valcheva - Nazurski was used. A technological regime: P in the beginning = 0.1MPa for technological time of 24h, as after visual evaluation of the opposite side of the sample wetting, the pressure is increased with 0.1MPa. The experiment is terminated at establishing of wetting. The experimental results proved, that at control samples the wetting appeared after 5x24h, i.e. at working pressure P= 0.5MPa The samples with TRPR additive at these conditions of time and regime were resistant. The samples with TRPR additives at these conditions for time and regime showed a good resistance. When the samples were cut, it was seen an equal distribution through the area of the control samples and a pulsating line with a height of 10mmon the active side, i.e. water reached half of the total height of the samples with TRPR additive. At detailed observation of all received and reported up results, it was established, that the addition of the thermo reactive, water-soluble composite to

BALWOIS 2008-Ohrid, Republic of Macedonia-27, 31 May 2008


the cement-sand or concrete mixture (cement : Sand : gravel = 1:2:2.46 and water : cement =0.45) is an effective technological decision, which grants high strength and anti filtration characteristics for the constructed hydro-equipment. This fact is especially significant for the purposes of the irrigation agriculture, where exist all preconditions for corrosive degradation (amortization) at the hydro-ameliorative and hydro technical equipments. DISCUSSION . ANALYSES The results from the experimental work proved, that the TRPR additive basically decides the problem with the porous structure of the concrete. It is known, that at hardening the concrete forms a structure, which includes a system of capillary and pores that predetermines the worsening of the discussed up exploitation characteristics. It was proved, that the possibility of the capillary to absorb, con duct and evaporate water depends on their dimensions, in which according the physical laws, is formed different in strength pressure of the saturated water vapors. It was established experimentally, that the capillary with a radius of 50 to 1000Ao (5x10-7 to 1x10-5cm) accumulated water from the air condensates in collimating effect, due to which the capillary even under pressure, do not transport water. At the experimental samples with polymer composite additive the porosity was measured with mercury pores meter type CE, and was obtained data about total pores volume and the distribution of the capillaries by dimensions- Table 3 and figures 1 and 2. After discussion of the received integral and differential curves the following conclusions can be made: 1. The total volume of the pores of the experimental samples with TRPR additive was established that the present capillaries are with total equivalent radius Re= 250 Ao, or 1.8 times lower than that of the etalon samples (without additive), which have total equivalent radius Re = 450Ao. 2. The compact structure of the concrete-polymer samples influences favorably the exploitation properties and it make possible the enlarging of their area of use in the practice. It is necessary, though, to admit that at contact with aggressive and neutral water in the structure of the experimental samples with TRPR additive, at hardening, formation of low basic calcium hydro- silicates highly dispersal and with big specific surface is possible, which leads to additional structure compaction. It can be supposed with a high probability also the formation of massive associates between the components of the composition, as the total volume of pores reach the equivalent radius of 300Ao (lower than that of the standard samples with ) and the experimental samples made of cement

BALWOIS 2008-Ohrid, Republic of Macedonia-27, 31 May 2008


plus TRPR-additive having equivalent radius Re = 240Ao in comparison with the equivalent radius of the standard samples, which is Re =450Ao.

CONCLUSION The experiments in this aspect are not as yet finished, but the data definitely can orientate the engineer- projectors to a suitable recipe composition, according the determined requirements and conditions for each hydro- equipment and its specific use. The scientific-applicable activity for creation and introduction of new construction materials and respective technological decisions aims at increasing the exploitation durability of the hydro- equipments, used in the irrigation agriculture, limiting the negative processes due to corrosion, overgrowing by plants and loss of useful irrigation water, due to filtration.

REFERENCES Fraser , P., (1981), The Science of the Total Environment., 18, pp. 103-116 Nikolova-Belcheva, B. L. Tzachevska, (1998), Polymer materials in Agriculture Economics and management in agricultural, 7, pp. 44-48 Nikolova-Belcheva, B. (2001), On the irrigation Agriculture State in Bulgaria, International conference and Seminar "BALKANERECO'02"S., Nikolova-Belcheva, B. (2001), Polyurethane Stuffs and Possibilities of Their Application in the Agriculture International Conference and Seminar "BALKANEIRECO'02"S.,

BALWOIS 2008-Ohrid, Republic of Macedonia-27, 31 May 2008