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Coventry University and

The University of Wisconsin Milwaukee Centre for By products Utilization,
Second International Conference on Sustainable Construction Materials and Technologies
June 28 June 30, 2010, Università Politecnica delle Marche, Ancona, Italy.
Main Proceedings ed. J Zachar, P Claisse, T R Naik, E Ganjian. ISBN 978 1 4507 1490 7

Grits as a Partial Cement Replacement for Concrete
M Luz Garcia1, 2, and Joana Sousa-Coutinho2

Porto Polytechnic Institute (IPP), Instituto Superior de Engenharia do Porto, ISEP - DEC, Rua
António Bernardino de Almeida, 4200-072 PORTO, PORTUGAL. E-mail: <>
Universidade do Porto, Faculdade de Engenharia do Porto, Departamento de Engenharia
Civil, LABEST/ FEUP, R Dr Roberto Frias, 4200-465 PORTO, PORTUGAL. E-mail:

The paper pulp industry produces several waste materials, most of which are dumped to landfill
causing economic and environmental problems. Grits is one such material and research is being
carried out on mortar, to ascertain applicability of Grits in concrete as a partial cement
replacement material.
As grits contain mainly calcium carbonate and amorphous material is absent, this waste material
will only act as filler. Therefore fineness is of the upmost importance and two sets of tests were
carried out with grits ground to different fineness. Strength and durability-related results of
mortar with 10% cement replacement by grits generally indicated relatively small differences to
control, improving with fineness.
Therefore if sulphates are controlled and chlorides reduced through prior treatment this waste
material, if ground to sufficient fineness may be used as filler for concrete. Applying grits even
in small dosages will avoid dumping and therefore contribute to sustainability in construction.

Cementitious materials, mainly in the form of concrete, are the most successful materials in the
world. Every year more than 1m3 is produced per person worldwide. The huge volumes of
cement and concrete produced mean that cement production accounts for some 5-8% of manmade CO2 emissions. Therefore there is increasing pressure to innovate to improve sustainability
[Scrivener and Kirkpatrick, 2008]. Concrete must keep evolving to satisfy the increasing
demands of all its users. Reuse of post-consumer wastes and industrial by-products in concrete is
necessary to produce “greener” concrete. Recycling by-products is an environmental-friendly
method for large quantities of materials that may otherwise pollute land, water, and air [Mehta,
The Kraft process (Figure 1) corresponds to a technology for conversion of wood into wood pulp
consisting of almost pure cellulose fibers for paper production. Grits are produced during the

. 2009] concerned examining the material per se. Grits are the insoluble materials removed from slakers after the reaction between green liquor and lime produced in this phase (slaker grits). Several tests were carried out such as chemical and . Grits have been used for soil stabilization [Pereira et al. 2006]. Fig. previously published [Garcia and Sousa-Coutinho. Flowsheet of the Kraft process under study EXPERIMENTAL PROGRAMME A first phase of the program.. 1. They are in particular. 2001] but not.a.clarifying process of black liquor which is recovered into white liquor needed for the digesting process of wood chips. 2009] and as sand replacement in mortar [Gemelli et al. to the authors knowledge. as cement replacement. as raw material for clinker [Castro et al. produced during the causticizing process which is part of the pulp mill chemical recovery circuit.

mineralogical analysis. resistivity and chloride ion penetration. The second study comprised grits material ground in a ceramic ball mill for 24 hours and named GRTb. Grits Fig. SEM – Scanning Electron Microscopy and laser particle size distribution. 3. Alkali silica and sulphate testing is also being carried out. Grits and Ground Grits Grits waste material was obtained from Portucel-Soporcel pulp paper industry plant at Cacia where they are deposited in controlled landfills (Figure 2). Los Angeles ground Grits (GRTa) GRTa . GRT > 250µm Fig. namely absorption by capillarity. 2. The second phase presented in this paper deals with durability – related properties of mortar with grits. Paper pulp industry plant and Grits Grits material was dried in an oven at 105 ± 5 º C. Grits consist of gray lime sludge with a Water Content of 15% to 25%. Mechanical properties were also determined in mortar produced with 10% replacement of ground grits. and then sieved and only particles under 250 micrometers were considered and named GRTa. resistance to accelerated carbonation. In a first study the waste material was ground in Los Angeles equipment.

Chemical Analysis presented by Cacia plant is shown in Table 2 and according to NP EN 196-2. it is shown in Table 3. SEM for cement used is also presented (Figure 7).GRTb Fig.5 R used. where it can be seen by comparing values in Table 4. Semi quantitative Mineralogical analysis of GRT Minerals Calcite Formula CaCO3 Portlandite Ca(OH)2 Sodic calcic Ca2Na2(CO3)3 carbonate Fig. Figures 8 and 10 show the particle size distribution of GRTa and CEM I 42. XRD and SEM X-Ray Diffraction revealed that this material does not contain amorphous matter and mineralogical analysis of Grits is shown in Figure 5 and Table 1. GRTb particles of intermediate size are scarce which is in accordance with the grading curve obtained by laser diffraction technique (Figure 9). that although GRTb is finer than GRTa. 4. this material should have been ground even further to fineness greater than cement for enhanced filling effect. 5. X-Ray diffraction of GRT % 92 1 7 . respectively. Table 1. Ball mill ground Grits (GRTb) Chemical analysis. SEM Scanning Electron Microscopy including EDS spectrums from different areas (Figure 6) disclose that GRTb particles are fairly homogeneous chemically.

01 0.17 0.02 0.Table 2.15 ± 0.31 ± 0. 0.36 0.004 0.008 ± 0.012 LOI Insoluble Residue SiO2 Al2O3 Fe2O3 MgO CaO Na2O K2O MnO SO3 Cl (%) 42 ± 2 1.07 39.11 ± 0.01 0.37 0.59 0.11 ± 0.3 12.40 ± 0.06 56 ± 3 3.02 EDS spectrum of GRTb particles (Figure 6) show predominance of calcium (Ca) and oxygen (O) and some sodium (Na) therefore in agreement with chemical analyses.69 0.26 0.9 94.3 0.q.07 < 1 l.0 ± 0.2 0.2 ± 0.6 5.81 0.1 87.03 0.4 0. Chemical analysis (NP EN 196-2) of GRT Average 3 Apparent density (g/cm ) % gross Humidity weight Solids (105+3º C) Fixed solids (550+25º C) Volatile solids (550+25º C) Total phosphorus (P) Sulphates (SO42-) Soluble sulphides Calcium (Ca) % Solids Magnesium (Mg) Sodium (Na) Potassium (K) Iron (Fe) Aluminium (Al) Manganese (Mn) Components 1. GLOBAL GRTb 200 times enlarged Spectrum for GLOBAL Z3 Spectrum for Z3 Z5 GRTb 1500 times enlarged Spectrum for Z5 Z8 Spectrum for Z8 .54 ± 0. Characterization of grits Factory Cacia Parameter Table 3.

186 16. SEM photos and EDS spectrums for GRTb GLOBAL CEM I 42. 6.31 GRTb Diameter (µm) 3.005 95.165 28.924 Fig.5 R 1500 times Spectrum for GLOBAL enlarged Z3 Spectrum for Z3 Fig.Fig.235 171.557 41. by volume) GRTa d10 d50 d90 9.081 18. 7. Laser grading curve for Grits (GRTa) CEM I 42. Laser particle size distribution curves (dXX-diameter for which XX% of the particles are smaller.5 R 2.354 . 8. SEM photos and EDS spectrums for CEM I Table 4.

Specimens were demoulded the next day and then cured in accordance with the standard procedure. Similar workability (CTL±10mm) was obtained for all types of mortar (Table 5). sealed bags was used. GRTa in the first step and GRTb in the second step. Laser grading curve for Grits (GRTb) Fig. . cubic and cylindrical test specimens were produced for the various tests to be carried out with each type of mortar. Laser grading curve for cement used MORTAR PRODUCTION Tests were carried out in two steps with two types of equivalent mortars being produced at each step. a control mortar (CTL) with 100% of Portland cement and a mortar with 10% cement replacement with ground grits. The ratio “binder: sand: water” for the all types of mortar was 1:3:0. Standardized CEN sand provided in 1350 gr. Workability was measured following the procedure described in ASTM C 109/90. 10. in water at 20 ºC.Fig.5 by weight. 9. Standard procedure described in EN 196-1 was generally used. Several prismatic.

which is a non-steady state migration method based on a theoretical relation between diffusion and migration. following the standard procedure described in NP EN 196-1. AI was determined at 90 days. produced in exactly the same conditions.Table 5. 28. Activity Index (AI) of a certain percentage of cement replacement by an addition corresponds to comparing strength of mortar produced with that percentage replacement with the strength of equivalent mortar with no cement replacement. 215. g Water. Results are shown in Table 6. Strength in compression Chloride ion penetration Chloride ion penetration was assessed by the Luping method. g 225 225 225 225 Flow. Flow test Mortar CTLa CTLb GRTa10 GRTb10 type CEM I 450 450 405 405 42. . g GRT.5 mm Density. Mixture proportions of mortars GRT CEM Fig. Strength and Activity Index Density at 7 and 28 days strength was determined at 7. 12. Results of this test are presented in Figure 14 and Table 6. 13.1±5. This method is based on measuring the depth of colour change of a silver nitrate solution sprayed on the specimens previously submitted to a migration test.9±7. Results are shown in Table 6 and Figure 12 and 13.1 219. This enables the calculation of the apparent chloride diffusion coefficient (Dns) from an accelerated test. at the same age.1 213. 11. 60 and 90 days.9±3.7 223.4±3. Strength in flexure Fig. Fig. g 45 45 Standard 1350 1350 1350 1350 Sand.5R.

Fig. Cell and Dns results for Luping method Fig. As only one test specimen for each mortar type was analysed. Capillary absorption for the first 4-1/2 hours .Resistivity Resistivity in saturated specimens was evaluated on specimens at the beginning of the chloride ion penetration test and results are shown in Figure 15 and Table 6. Resistivity Absorption by Capillarity Water absorption by capillarity was carried on 150 mm cube specimens on a 3mm water layer. 16. Fig. 16. 14. 17 and Table 6) with correlation coefficients (R) over 0. 15. Carbonation Accelerated carbonation tests were carried out following the procedure described in LNEC E391. results shown in Table 6 must be considered cautiously. Specimens were weighed at time intervals up to 4h 30min and linear regression was applied to the plots leading to sorptivity results (Figs.998.

6 -34% -14% 66% 86% .6 7.6 ± 2.4 7. 7d MPa Compressive strength.7 -27% -23% 8.7 9.4 ± 0.9 ± 0.2 ± 1.4 6. MPa 7d Density.5 ± 2.6 -4% -18% 2274 ± 23 2312 ± 14 2293 ± 6 2302 ± 28 8. (+/-) .6 ± 0.2 ± 0.8 ± 0.5 10.0 ± 0.8 37.9 42.2 ± 1.6 31.6 ± 1. 28d kg/m3 Flexural strength.0 ± 0.2 ± 1.3 11. 28d MPa Compressive strength.4 ± 2.8 32. (+/-) of of GRTb10 GRTa1 GRTb1 0 0 versus versus CTLa CTLb Density.6 ± 0.3 -22% +9% 60.2 ± 0.3 -13% +8% 34.Fig. 60d MPa Compressive strength.5 12.6 8.0 ± 1.7 8.0 ± 1. Mortar type CTLa GRTa10 CTLb Perfom Perfom .8 ± 0.6 38. MPa 60d Flexural strength.6 41. 7d kg/m3 Flexural strength. 17. strength and activity index (AI) Density.8 -7% -11% 49. Mechanical and durability results obtained for the two sets a and b each with two mortar types (CTL and GRT) as well as perfomance (+ or -) of each property for GRT mortar versus the value of property obtained for CTL mortar.9 52.8 39.2 40. Sorptivity Table 6.5 ± 2.6 ± 3.1 ± 0. MPa 28d Flexural strength.2 ± 1. 90d MPa Compressive strength.1 ± 0.9 ± 0. MPa 90d AI % Durability related properties 2268 ± 21 2279 ± 6 2343 ± 29 2382 ± 17 7.2 ± 0.2 6.8 ± 2.2 ± 0.2 61.1 -21% -13% 11.5 54.

.3 Dns.5 ± 0. P. (1990). 81d Ohm. C. J. (2009). D. Castro. F. F. ACKNOWLEDGMENTS The authors would like to thank Portucel-Soporcel. “Test Method for Compressive Strength of Hydraulic Cement Mortars. Materials Engineering Innovation.2 ± 0.6 ± 0. Except for sorptivity.5) 4. pp.1%) through prior treatment this waste material. and Miragaia.9 53. durability related properties show similar performance for both GRT mortars compared to CTL. “Utilisation of pulp and paper industry wastes as raw material in cement clinker production”.. 81d m2/s Resistivity.. Int.0 -298% -18% m2 09 17 05 04 ×min0.2 ± 0.7 12. XCTL – test for CTL mortar CONCLUSIONS Grits material consists mainly of calcium carbonate with no amorphous material and therefore non pozzolanic.5 +3% mg/(m 0.061±0. Vilarinho. ×10 -12.m Sorptivity. 1. Vol1. with enhanced performance for finer material.243±0.0 ± 1.3 ± 1. REFERENCES ASTM C 109/90.7 ± 0. 47d -10% 16. Therefore as a first conclusion if sulphates are controlled and chlorides reduced (to under 0.” ASTM Designation C109-90-Standard.4 4.5 ±0.. 28d Ohm.. Trancoso.5 -4% +3% 38.7 ± 0.7 ± 0.0 0.2 39.11..061±0. 28d m2/s Dns.7 16. ×10 -12. A.m 52. Although strength for GRT mortar was always under CTL it did increase with fineness thus presuming similar performance to CTL with further grinding.4 4.5 Resistivity.8 -11% -5% mm XGRT – test for GRT mortar. ..0 ± 1. Ferreira. No. to RAIZ and also to the MsC students Antonio Silva and Gabriel Santos.0 0. Nunes.4 4. if ground to sufficient fineness may be used as filler for concrete. Applying grits even in small dosages will avoid dumping to landfill and therefore contributing to sustainability in construction.0 0. 36d Carbonation.0 ± 0.072±0. 74-90.

R.pp. 38: 9. Materials Research.Garcia.4. 6-9 Sept. pp. M.. J. R. Portugal. IPQ. Nocmat2009.30 nº4. Vol. Machado. P. K. Portugal. Portugal. C. (2001). Estacionário.A. UK Gemelli. (1996). LNEC. (2009). (2006).A. Bath.H. NP EN 196-1.. Lisboa. N.4. ASCE. “Innovation in use and research on cimentitious material. No. “Métodos de ensaio de cimentos – Parte 1: Determinação das resistências mecânicas”: IPQ.” Ed. (2008). ISSN 0100-6762Ed. Brasil Scrivener.“Evaluation of Paper Industry Wastes in Construction Material Applications”.”.an overview of recent developments. (1993). Ver.” Cement and Concrete Research. “Betões. Determinação da resistência à carbonatação. Mehta. “Grits and Dregs for cement replacement – Preliminary studies”. 11th International Conference on Non-conventional Materials and Technologies Materials for sustainable and affordable construction (ICNOCMAT 2009). . J. “Métodos de ensaio de cimentos – Parte 2: Análise química dos cimentos. 243-256. Durham.C.L..J. (1994). 297-304. Árvore vol. C.. and Kirkpatrick.” Ed. Camargo.K.S. NP EN 196-2. and Brescansin. Mineral admixtures for concrete . and Sousa-Coutinho. Proceedings of an Engineering Foundation Conference: Advances in Cement and Concrete. (2006). Pereira. LNEC E 391. E. and Carvalho. “Aplicações de misturas solo-grits em estradas florestais: resistências mecânicas via CBR.L..