Construction and Building

Construction and Building Materials 21 (2007) 578582

MATERIALS
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New construction material from concrete production and demolition wastes and lime production waste
V. Mymrin *, S.M. Correa
Chemical Engineering Department, Federal University of Parana (UFPR), Centro Politecnico, Curitiba, 81531 990 Parana, Brazil Received 14 June 2005; received in revised form 7 September 2005; accepted 19 September 2005 Available online 15 November 2005

Abstract New construction materials were developed and patented in Brazil, based on concrete production and demolition wastes mixed with lime production waste. The main objective of this research is to utilize these two types of industrial wastes on as large a scale as possible as a new raw materials for the production of concrete. The lime waste is characterized by a high content of SiO2, Al2O3, CaCO3 and other elements. After 90 days of aging in open air, the water absorption value of the sample mixtures was 12% and the uniaxial compression strength reached up to 33 MPa, with an average of 29 MPa. XRD and SEM analyses of the compositions reveal various reasons for the materials increased strength, including transformation of the initial mineral mixture (lime and Portlandite) into calcium, magnesium and amorphous ferrous and crystalline carbonates (Calcite, Dolomite and Ancerite), and chemical interactions of the concrete waste with the lime component, which led to the growth of new amorphous and crystalline calcium hydrosilicates such as Tobermorite, Afwillite and the CSH mineral group. Although this research does not include an economic feasibility study, the zero cost of these novel raw materials for concrete is self-explanatory. However, the main advantage expected from these materials is the environmental conservation they aord, represented by the use of concrete production and demolition wastes and lime production waste. 2005 Elsevier Ltd. All rights reserved.
Keywords: Concrete production and demolition wastes; Lime production waste; Physicochemical interaction; Strengthening; New structure formation

1. Introduction The earliest accounts of construction and demolition wastes (CDW) used as raw materials date from ancient Roman times [1]. Research in this eld began in 1928, but the widespread use of these materials only began in earnest in Europe after the end of World War II, in the reconstruction of cities destroyed by the war [2]. Europe today dumps nearly 200 million tons of concrete and rock debris annually. This quantity suces for the construction of a six-lane road connecting London to Rome [3]. The quantity of CDW produced in many countries varies from 136 to 3359 kg/inhabitant/year [4,5], which is esti-

Corresponding author. Tel.: +55 41 3361 34 25. E-mail address: seva@ufpr.br (V. Mymrin).

mated to represent 1380% of the entire mass of municipal solid wastes [6]. Oerman [7] analyzed the feasibility of replacing natural aggregates with CDW destined for the production of concrete. To reduce the water absorption of small CDW particles, he replaced a granulometric fraction of less than 4 mm with natural sand. Hansen [8] demonstrated it is possible to produce new concrete from concrete waste, without requiring new cement, by adding y ash, with the novel concrete containing 79% of concrete waste, 11% of y ash and 10% of water. Although the development of new composites from CDW combined with other industrial residues oers economic and environmental advantages, all current research is devoted to the use of construction or demolition wastes combined with Portland cement. The literature contains no report about the use of lime as a binding component,

0950-0618/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.conbuildmat.2005.09.007

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much less about the use of lime production waste. The research strategy of the Laboratory of Environmental Technology (LTA), Federal University of Parana (UFPR), is based on the use of 100% waste material, i.e., concrete production and demolition waste (CPDW) and lime production waste (LPW), to be developed as a raw material for concrete. 2. Objectives of the research

Table 1 Compositions of the mixtures under study No. Samples composition, weight % Concrete waste 1 2 3 4 5 6 7 90 85 80 75 70 65 60 Lime production waste 10 15 20 25 30 35 40 Water 10 15 20 25 30 35 40

1. Develop composites for the production of new construction material from CPDW and LPW. 2. Study the physicochemical properties of the best composites and verify if they meet the requirements of Brazilian construction standards.

3.3. Compressive strength Measurements were taken of the uniaxial compressive strength of six samples of each composition. The average results obtained are listed in Table 3, as is the average deviation. All the compositions showed steadily increasing strength, with almost no visible digressions, up to nearly 29 MPa in the 90-day aging period. The strength of the material increased along with the lime content. Therefore, the best result was achieved with composition 7, which had a 40% lime content. However, the dierence in strength between composition 7 (28.97 MPa) and compositions 6 and 5 (27.46 and 26.03 MPa, with 35% and 30% of lime content, respectively) was not signicant. From a cost standpoint, however, the latter two compositions may be utilized in industrial applications. The data in Table 4 indicate that the water absorption values of the composites under study varied from 10.38% to 12.99%. The best water absorption value (10.38%) was displayed by composition 7, which contained 40% of LPW. 3.4. Physicochemical strengthening of the materials An XRD analysis of the mineralogical composition of the initial dry mixtures of the wastes revealed the presence of the following groups of minerals:
Table 2 Chemical composition of the raw materials under study (by XRF method) Elements Compositions and analysis error, weight % Concrete waste Lime production waste A.E. 0.1 0.06 0.03 0.03 0.02 0.01 0.02 0.01 0.01 0.005 0.004 Compos. 2.82 47.69 0.25 0.24 33.10 0.05 0.03 0.04 0.02 15.74 100 A.E. 0.02 0.07 0.008 0.008 0.06 0.002 0.002 0.003 0.001

3. Methodology 3.1. Sample preparation Representative samples of CPDW and LPW were collected, dried, ground, sieved through a 1.18-mm mesh sieve and used only fraction 61.18 mm. After dierent percentage compositions (Table 1) of the wastes were homogenized, they were hydrated with a 1:1 ratio between lime and water because of high CaO content in the LPW. The hydrated samples were allowed to rest for 40 min and then compacted. The compaction process was performed in two stages: they were preloaded to 15 MPa, then unloaded and subjected to a second load of 30 MPa. The compacted cylindrical (2 2 cm) samples were stored in open air with temperature 2535 C and relative humidity 6575%. Water absorption capacity tests were carried out in line with Brazilian standards [9] and were calculated according to the following formula: W abs M humid M dry =M dry 100%; where Mhumid is the mass of the sample after 72 h of saturation in water and 5 h in a boiling water bath; Mdry is the mass of the sample after 72 h of drying at a temperature of 105 C. 3.2. Research methods The results were analyzed by XRD, XRF, SEM, Atomic Absorption Analyses (AAA), uniaxial compressive strength and water absorption. The main components of concrete waste are SiO2, CaO and Al2O3 (Table 2). Lime waste contains mainly CaO and MgO in a total content of only 80.79%, with a high content (18.74%) of underred limestone. Brazilian building standards [10] require this total to be no less than 8890%. Therefore, this product cannot be sold as construction material but must be classied as industrial waste. It is normally used to neutralize acid soils or is consigned to industrial dumps.

Compos. SiO2 CaO Al2O3 Fe2O3 MgO K2O SO3 Na2O TiO2 P2O5 MnO C Total 55.82 21.7 8.47 3.69 3.13 2.51 2.31 0.74 0.67 0.16 0.09 100

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Table 3 Compressive strength of the new materials No. Statistical parameters Samples strength after hardening (days) 3 1 2 3 4 5 6 7 Average Deviation Average Deviation Average Deviation Average Deviation Average Deviation Average Deviation Average Deviation 7.27 0.58 9.04 1.34 8.53 1.43 12.71 2.68 15.91 1.57 16.49 2.08 15.12 4.48 7 8.89 0.92 9.11 1.86 9.94 1.72 14.88 1.00 18.29 1.32 18.10 1.23 16.47 3.99 14 8.88 1.33 9.61 1.51 11.06 0.80 14.76 1.16 19.72 2.75 19.69 2.31 20.51 1.96 28 10.13 1.33 10.96 2.37 11.66 1.27 15.48 2.17 18.35 2.46 21.10 1.78 19.50 3.01 60 12.33 1.03 13.01 1.61 15.71 1.00 21.42 1.90 24.12 1.32 26.07 2.60 25.18 4.37 90 13.84 0.71 16.31 1.42 18.58 2.65 22.14 2.00 26.03 3.41 27.46 1.83 28.97 3.25

 natural components of concrete waste aggregates Quartz (SiO2), Microcline (KAlSi3O8), Orthoclase (KSi3AlO8), Calcium Carbonate (CaCO3) and Calcium Silicate (Ca2SiO4);  products of hydration Afwillite Ca3(SiO3OH)2 2H2O, CSH Calcium Silicate Ca4Si5O13.5(OH)2 and Calcium Silicate Hidrates (Ca1.5SiO3.5 xH2O);  binding materials, such as and Lime (CaO), Periclase (MgO), Calcium Hydroxide Portlandite Ca(OH)2;  carbonate Calcite Ca(CO)3. Table 5 compares the changes in some of the peak intensity positions during the hydration of the initially dry mixture (3, 28 and 90 days). The diractograms of samples after the rst 3 days of hydration reveal the disappearance of the lime peaks (d = 2.777 A) and Portlandite (3.104 A) and the appearance of material hydration products such as Tobermorite (Ca5Si6O16(OH)2) at d = 3.186, 2.628,

Table 4 Water absorption of CPDW and LPW composites No. Statistical parameters Weight after 28 days (g) After 72 h of drying 1 2 3 4 5 6 7 Average Deviation Average Deviation Average Deviation Average Deviation Average Deviation Average Deviation Average Deviation 13.30 0.03 13.30 0.028 13.28 0.020 13.29 0.05 13.30 0.05 13.12 0.19 13.51 0.33 After water bath 14.96 0.01 14.86 0.04 14.82 0.02 14.82 0.068 14.89 0.046 14.82 0.24 14.92 0.26 12.47 11.76 11.56 11.50 12.00 12.99 10.38 Water absorption (%)

1.817, 1.798 and 1.604 A, Ancerite Ca(Mg, Fe)(CO3)2 at d = 2.897, 1.8182 and 1.452 A and the appearance of many additional peaks of Calcite Ca(CO)3 at d = 3.852, 3.032, 2.494, 2.280, 2.104, 1.916, 1.8741 and 1.604 A. The diractogram taken on day 28 showed Dolomite CaMg(CO3)2 peaks at d = 2.403, 1.818 and 1.793 A, while the diractogram after 90 days of aging again showed all the minerals that had already appeared before, indicating that synthesis occurred during the hydration process, improving the crystal lattices of the calcium carbonates Calcite, Dolomite and Ancerite. Such carbonates synthesis is quite usual for the lime-based materials. Only two of these carbonate peaks did not coincide with the peaks of the other minerals, i.e., Calcite at d = 3.856 and 2.494 A. However, the intensity of these peaks in the diractograms showed an increase of only 0.98% and 1.08%, respectively, while the other minerals showed practically the same crystal growth peak intensities. The SEM micrographs (Figs. 1 and 2) revealed amorphous new formations. Mymrin [1113] observed similar forms on the surfaces of mixtures of clayey soils with ferrous slag in a study of their chemical interaction and structural formation. The samples attained strength of 50 MPa, and the X-ray diractograms revealed no crystal structures. After exhaustive research by various methods, Mymrin concluded that the high strength of his material could only be explained by the solgel strengthening of amorphous new formations. Our analyses of the various compositions under study here suggest that they also possess quite large amounts of amorphous new formations which act as binders, causing the concrete waste to cohere. Mehta and Monteiro [14] reached a similar conclusion from their study of a new colloidal CSH formation of Portland cement. The most conclusive analytical method employed in these studies was SEM. The SEM micrographs clearly show the concrete waste structure (Figs. 1(a) and (b)) containing inclusions of

V. Mymrin, S.M. Correa / Construction and Building Materials 21 (2007) 578582 Table 5 Change of mineral compositions of the materials under study during their hardening XRD-peaks positions description during hydration after (days) Initial, dry d (A) 3.856 3.186 3.104 3.031 2.896 2.777 2.628 2.494 2.404 2.280 2.106 1.923 1.875 1.817 1.798 1.673 1.604 1.452 3 Int. (%) 0.52 1.72 0.70 4.87 0.81 1.93 3.74 0.44 5.22 6.62 12.55 1.36 0.50 8.74 1.35 1.90 0.10 1.80 d (A) 3.864 3.187 3.035 2.897 2.630 2.495 2.403 2.283 2.108 1.920 1.876 1.818 1.797 1.672 1.603 1.452 Int. (%) 1.22 5.66 12.69 1.14 1.94 0.96 3.80 6.85 10.22 1.60 1.33 11.71 1.21 3.18 0.50 0.83 28 d (A) 3.852 3.185 3.032 2.898 2.624 2.494 2.403 2.280 2.104 1.916 1.874 1.818 1.793 1.672 1.604 1.451 Int. (%) 1.36 1.57 13.17 1.20 2.31 1.17 4.13 6.12 8.85 1.98 1.87 5.96 1.23 2.26 0.55 0.78 90 d (A) 3.852 3.188 3.034 2.897 2.626 2.493 2.404 2.280 2.106 1.927 1.878 1.817 1.796 1.671 1.605 1.451 Int. (%) 1.59 1.79 13.94 1.28 5.14 1.42 5.25 12.40 11.49 2.41 1.95 24.80 1.81 3.41 0.67 1.31 Matched by minerals

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Calcite Afw., Tb 3.104 3.031 2.896 2.777 Prtld; Tb; CSH Calcita Lime; Dolomite; Ort. Q; CS; CSH; Calcite; Afw Periclase; Calcite; Tb Calcite; Prtld; CS; Tb; Afw Calcite; CS Q; Tb; Dlm; Ancerite; CSH Q; Afw; Prtl; Dolomite Q; Ortoclase Q; Calcite; CSH; Afw; Tb Lime, Q; Ort; Prtld; Ancerite

Q, Quartz (SiO2); Prtld, Portlandite Ca(OH)2; Periclase, MgO; Dolomite, CaMg(CO3)2; Ort, Ortoclase KSi3AlO8; CS, Calcium silicate Ca2SiO4; Calcite, CaCO3; Anc, Ancerite Ca(Mg Fe)(CO3)2; Mcr, Microcline KAlSi3O8; CSH, Calcium silicate hydrate Ca2SiO4 H2O; Tb, Tobermorite Ca5Si6O16(OH)2; Afw, Afwillite Ca3(SiO3OH)2 2H2O.

stone and sand aggregates. Their surfaces are covered with amorphous formations and are devoid of crystal bodies.

This type of structure remained preponderant (Fig. 2(a)) throughout the compositions hydration and interaction, although crystal druses (incrustations) appeared at a few

Fig. 1. Micrographs of initial mixture before the hydration.

Fig. 2. Micrographs of the new material originating from concrete waste and lime production waste after 90 days of hydration.

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surface points (Fig. 2(b)). This nding conrmed the XRD data about the partly crystalline nature of the new formations, which strengthened the materials volume. 4. Conclusions 1. This research provided experimental conrmation of the promising potential of new construction material using as raw material concrete production and demolition wastes mixed in dierent proportions with lime production waste. 2. All the compositions under study demonstrated good mechanical properties (uniaxial compressive strength and water absorption), in line with the requirements of Brazilian standards. The best mechanical properties were obtained for the composition containing 40% of lime waste and 60% of concrete wastes, showing an average strength of 26 MPa after 90 days of hydration. The mechanical properties of compositions 5 and 6, containing 30% and 35% of lime waste, respectively, indicate their competitiveness with composition 7. Moreover, other compositions can also be applied for dierent construction purposes. 3. The XRD and SEM analyses indicated that the following processes occurred during the hydration and hardening of the original compositions:  Complete transformation of lime (CaO) and partial transformation of Portlandite Ca(OH)2 into various carbonates forms, e.g., Calcite CaCO3. Dolomite CaMg(CO3)2 and Ancerite Ca(Mg Fe)(CO3)2.  Synthesis and enhancement of crystalline structures Tobermorite Ca5Si6O16(OH)2, Afwillite Ca3(SiO3OH)2 2H2O, and Calcium hydrosilicates (CSH) CaO SiO2 H2O.  Growth of a signicant number of new amorphous formations, which were clearly visible with SEM, especially under high magnication. The synthesis of these three groups of new formations likely explains the substantial increase in the strength of the concrete and lime waste composites. 4. Although our research objectives did not include an economic feasibility study, there is no doubt that the use of industrial wastes as cost-free raw materials will represent substantial savings for civil construction. 5. The application of these readily available industrial wastes as raw materials for civil construction will translate into signicantly reduced environmental pollution.

Acknowledgements The authors are indebted to Prof. Haroldo A. Ponte, the founder of Environment Technology Laboratory (LTA), who invite me to continuer my researches in UFPR and his nancial support of my participation in EUROMAT2005; UFPRs Laboratories of Mineralogy (LAMIR) and of Materials and Structures (LAME) and to the Institute for Technological Development (LACTEC) of Curitiba, PR, Brazil for their generous support of this work; CNPq for strong nancial assistance of my participation in EUROMAT-2005. References
[1] Petrucci EGR. Materiais de Construcao. 2a edicao. Editora Globo; 1976. [2] Levy SM, Helene PRL. Reciclagem de Entulhos na Construcao Civil a Solucao Poltica e Ecologicamente Correta. In: Simposio Brasileiro de tecnologia de argamassas, 1 Goiania, Brasil; 1995. p. 31525. [3] Laguette MJ. Reciclaje: la clave para la conservacion de recursos. construction Pan-Americana, julho; 1995. [4] John VM. Reciclagem de resduos na construcao civil contribuicao ` a metodologia de pesquisa e desenvolvimento. Universidade de Sao Paulo; 2000. 102p. [5] Pinto TP. Metodologia para a gestao diferenciada de resduos solidos da construcao urbana. Universidade de Sao Paulo; 1999. 189p. [6] Angulo SC. Variabilidade de agregados graudos reciclados de resduos de construcao e demolicao reciclados. Dissertacao (Mestrado); Escola Politecnica, Universidade de Sao Paulo; 2000. 155p. [7] Oermann, EHO futuro da reciclagem de entulho de construcao (traducao). Hochschuljournal Essen, no. 52; 1987. [8] Hansen C. Recycled concrete aggregate and y ash produce concrete without strength cement. Cement Concrete Res 1990;20(3):3556. [9] Associacao Brasileira de normas tecnicas, NBR 9778. Argamassa e concreto endurecidos Determinacao da absorcao de agua por ca. imersao ndice de vazios e massa espec [10] Associacao Brasileira de normas tecnicas, NBR 6453. Cal virgem para construcao civil Requisitos. [11] Mymrin VA. Investigation of hardening processes of dusted dump blast-furnace slag. Bulletin of Moscow Society of Nature Researcher, Section of Geology, Moscow, vol. 55; 1980. p. 121. [12] Mymrin V.A. Activation of the blast-furnace dump slag by small addition of lime or Portland cement. In: Proceedings of the XI Poland conference on soil mechanics and foundation, Warsaw, Poland; 1981. p. 498503. [13] Mymrin VA, Ponte HA, Yamamoto CI. Synthesis of colloidal new formations during the strengthening of dierent activated hydrated metallurgical slag. Colloid Surf A 2003;220(13):21121. [14] Mehta PK, Monteiro PJM. Estrutura, propriedades e materiais. PINI, Sao Paulo; 1994.