Understanding the Powdered Silica Fume

Syed Ali Rizwan1, Gert Schmidt2 and Thomas A. Bier2 Abstract The powdered silica fume has been used quite often in the developed world for making high performance concrete (HPC) and self-compacting concrete (SCC). However there is a trend in using silica fume to achieve higher concrete strength in developing countries without knowing its complete characteristics, mix proportions, aggregate grading and environmental conditions during placements. Silica fume seems to be an interesting pozzolanic mineral admixture known for improving the concrete microstructure and its anti-bleed properties. However the underlying mechanism is still not very clear. An attempt is made to provide some information regarding this characteristic of powdered silica fume. It appears that the role of carbon particles and that of agglomerated silica fume particles may be the underlying mechanism regarding the anti-bleed properties of silica fume. 1. NUST Institute of Civil Engineering (NICE), National University of Sciences & Technology (NUST), Islamabad, Pakistan. syedalirizwan@hotmail.com, Member ACI Committees 237, 234 and 232. 2. IKGB, Technical University Freiberg, Germany. gert.schmidt@ikgb.tu-freiberg.de, Thomas.bier@ikgb.tu-freiberg.de Key Words: Silica fume, high-performance concrete, mercury intrusion porosimetry, Superplasticizer and shear rate. Introduction The modern concrete systems including HPC and SCC usually possess high powder content with low w/cm ratio. In order to make them environment friendly and to avoid related problems, usually a part of cement is replaced with secondary raw materials (SRMs) and especially with silica fume (SF) which seems quite popular amongst construction technologists especially in developing countries. The addition of SF increases the rate of early hydration due to release of OH- ions and alkalis into pore water fluid which provides ability to provide nucleation sites to products of hydration sites for CSH and ettringite(1). SF increases hydration of C3S and C3A in early hours of hydration (1). SF tends to affect the pattern of crystallization and degree of orientation of CH crystals during first few days of cement hydration (1). Rao (1) states that at 30% SF addition false setting of cement paste was observed. Highly crystalline portlandite (CH), and amorphous CSH are formed in the hydration of Portland cement(PC) and the hydrated cement paste consists of approximately 70%CSH, 20% CH , 7% sulphoaluminates and 3% secondary phases (2). Cement paste containing SF produces amorphous CSH gel with high

density and low Ca/Si ratio. (2). It has been reported that in a mixture of 70%PC and 30% SF , CH disappeared entirely(2). CH also decreases when SF and FA are used together (2). Silica Fume , because of its extreme fineness, penetrates between cement grains and decreases watercement ratio in the given volume(3).There seem to be co-relations between some secondary constituents of silica fumes(C, Al2O3, Fe2O3, MgO and Alkalis) , the contents of which increase as the quantity of silica (SiO2) and after analysis it can be found that only carbon and alkalis are the important components determining the strength development (3) which proposes the following relations for two different series. Fc = 173.8 -2.11C Fc= 194.7 2.81 C (1) (2)

Where Fc (kN) is the mean compressive force at failure for 40x40 mm specimens and C is the percentage of carbon in the silica fume. For the flow time increases with increase in the Carbon content and density decreases with the increase in flow time (3). Literature states that a reduced porosity and the presence of many more hollow shell pores (1-15 microns) are present during early hydration(but persist later on as well) of cement with SF due to cement grain dissolution in the gel when SF replaces a part of cement. These pores appear to be connected to continuous capillary pore system by means of smaller gel pores (4). In order to utilize SF effectively in concrete, its characteristics must be known in order to avoid running into a very big mess later on during and after construction. There may be problems related to temperature rise, Autogenous shrinkage and possible early cracking. It has been found (6) that the Autogenous shrinkage in concrete with low water-cement ratio is the major factor for early age cracking. SRMs and especially SF have a significant impact on the ability of concrete to resist the penetration of chloride ions, resisting alkali-silica reaction and other deleterious actions which are related mostly to the quality of microstructure (7) The above discussions force the reader to think about the following questions. 1. Why/how silica fume acts as anti-bleed SRM? 2. Which constituents of silica fume may be responsible? 3. Why there is intense heat liberation in the calorimetric investigations during the early hydration stages? 4. What is the role of silica fume on the fresh and hardened properties of concrete and especially HPC/SCC? It may be possible that the role of carbon and that of agglomerated silica fume particles is responsible for this phenomenon. Carbon can always be found in the silica fume. The origin of carbon comes from the production process shown in Fig.1

Fig 1. Manufacture Process of Silica Fume.

Carbon Content in Silica Fume Different types of carbon containing materials perform as reducing agents (coal, brown coal, wood charcoal etc.). The carbon particles are much bigger than the silica fume particles (see figs. 2(a) to 2(E) and are irregular in shape and these seem to contain a morphology which seems to encourage the intake of fluids. The carbon not only influences the color of SF, but also its content, size and the origin of its particles seem to have an effect on the properties of silica fume. Also a nearly white silica fume contains certain content of carbon which seems to influence the surface reactivity of the silica fume (10, 11).The carbon content of the silica fume is an indicator of the state of aggregation of the grains, with a high carbon content showing a coarser granularity and the grading governing the flow time (depends on air content as well) of mortar. It may be possible that such carbon particles accommodate mercury/water during MIP and mixing respectively. During setting process, alkalis released by cement and silica fume control hardening kinetics of the mixture and high alkalis favor cement hydration while opposite may be expected for SF hydration. In nut shell, the carbon content of a silica fume, shown by its color, is

a good indicator of its quality i.e. low carbon content imparts a light grey color in SF particles and translates into more fluidity and higher strengths (3). Study on Pure SRMs indicated that significant amount of mercury gets intruded in the SF sample as evident from the MIP measurements (5, 8). It is known to materials engineers that 95% of SF particles have a size less than 1 micron, a bulk density in the range of 130-430 kg/m3 for as produced micro silica, a specific gravity of around 2.2 and BET area of 13000-30,000 m2/kg. SF usually accelerates the C3S, C2S and C4AF hydrations while it reduces bleeding and segregation, generates heat of hydration even in the replacement mode (optimal replacement of 10%).It may be kept in mind that HPC /SCC containing SF suffer higher strength losses due to temperature. SF decreases thermal conductivity and creep strains while it increases plastic and Autogenous shrinkages. Experimental SEM and MIP techniques were used to investigate the characteristics of silica fume particles. Table A in appendix shows the properties of a typical silica fume. It had LOI of 1.2%, free Carbon 0.6%, pH of 7.5 primary particles 0.1-0.3 microns with secondary agglomerates of size greater than micron were 30%, greater than 10 microns of 5% and greater than 45 microns of 1.5%. The particle size distribution and properties vary but only slightly for different types of silica fume grades like 971 U, 920D and 968 U of Elkem. The Characterization of carbon particles in SF

Fig.2 (a) Carbon Particle in Silica Fume

Fig. 2(b) Another type of Carbon Particle in Silica Fume

Fig.2 (C) Another Type of carbon Particle in Fig 2 (D) Another form of carbon particle in silica fume. silica fume.

Fig. 2 (E) Another form of carbon particle in silica fume Fi.2 Different types, shapes and surface morphologies of carbon particles found in Silica Fume To look into the anti-bleed properties and anti-segregation properties of SF, it was thought to perform MIP test on various powders including SF. Fig 3(a) shows the partial MIP diagram while Fig. 3(b) shows the cumulative diagram of MIP on powders. Fig.3(c) shows the SF particle morphology obtained using SEM technique. When doing SF particle characterization by Laser granulometry, the average size (D50) of SF particles determined (around 6-14 microns) is that of the primary group of fused SF particles shown in Fig.4 and not that of single particle which is in nanometers.

Fig.3(a) Partial Diagram of Fig.3(b)Cumulative Diagram Fig.3(c)Silica Fume (Rizwan SRMs (Rizwan 2006) of SRMs (Rizwan 2006) 2006) Fig 3(a) and 3 (b) are interesting and form the basis of thinking process. In fig 3(a), at 57.94 nm average pore radius of SF particles, about 5.507 cc/g of mercury is intruded. The question is where such an amount of mercury is accommodated in SF particles? Then in Fig 3(b) mercury intrusion in SF particles starts at 2374.9 nm where 6.65% mercury is intruded. Then almost smooth mercury intrusion takes place up to SF particle size of 69.94 nm wherein 66.41% mercury has intruded. This smooth intrusion may be due to some kind of connectivity between particles, due to small gaps and in the carbon particles in the primary group of SF particles. Fig. 4 shows TEM pictures of the primary SF group.

Fig.4 TEM image of silica fume primary group of particles ( See their fusion and connection)

Thereafter comes the rising part in Fig 3(b) indicating connectivity due to possible breaking of small sized SF particles near applied pressures of about 350 MPA plu. This part terminates at 43.9 nm particle size wherein about 89.5% mercury is intruded and just after that it appears that due to excessive applied pressure during MIP, the SF particles start breaking resulting into almost entire per cent mercury intrusion. It is obvious from Fig.4 that it is almost impossible to separate the SF particles in the primary group even after the application of high shear rates and therefore the particle size (D50) of SF as given by the Laser granulometry is not that of single SF particle but it is of the primary group of agglomerated SF particles. The actual idea of the particle size may best be obtained either by SEM or TEM process. There is some percent of carbon in almost all SF samples and this is given in the technical data sheet of the manufacturer and is annexed in this paper. Carbon particles are irregular in shape and quite massive in size. Table 1 gives the physical and chemical properties of powders. Table No 1. Parameters Specific gravity Particle size (d50),m BET surface Areas, m2/g Physical and Chemical Composition of Powders CEM I 42.5 R SF 3.1552 2.3560 18.42 12.16 1.098 Chemical Analysis Loss on ignition Silicon Dioxide Aluminum Oxide (wt, %) Ferric Oxide Calcium Oxide Magnesium Oxide Sulfur Trioxide Sodium Oxide Potassium Oxide 20.457

2.75 19.17 5.21 2.39 61.12 2.78 3.30 1.25 1.01

1.6 95% 0.2 0.05 0.25 0.4 0.1 1.2

It can be seen that the Table 1 indicates the size of SF as 12.16 microns which the size of inseparable SF particles in the primary group.

Interconnection between SF Particles

Fig 5(a) TEM picture showing SF Powder- Fig 5(b) TEM picture showing SF powdershowing circular particles of varying sizes. Primary groups are seen Figures 5(a) and (b) are TEM representations of SF particles. Several properties of SF including the particle size, their connectivity and the morphology can be seen. These figures indicate that small particles tend to stick to a relatively larger particle within the primary group. The particles are round and of smooth surface.

Fig.6(a) Shrinkage Response of SCP mixes.

Fig 6(b) Calorimetric Response of SCP mixes.

Fig. 6(a) shows the early shrinkage response of two SCP formulations. It can be seen that cement paste containing 10% replacement of SF shows much faster and higher shrinkage than the pure self-compacting paste at almost similar Vicat setting times. This shrinkage is thought to be brought about by the consumption and uptake of water by the SF particles indicating that water is being held somewhere or is being consumed at a faster pace in the cement formulation containing SF. This may be due to reduced effective water-cement ratio which decreases the distance between cement grains. This idea is strengthened in the fig. 6(b) which shows the Calorimetry curves of self-compacting paste systems (SCP). It can be seen that SCP system containing 10% replacement SF shows much higher and earlier peak with reduced dormant

period. The dots on curves are Vicat final setting times of respective formulations. Such a setting time (time-zero) sits either at the peak or start of acceleration period. Such systems were tested for flow, strength and microstructure and the details are available in (8).However Fig 6 clearly shows that when SF replaces 10% CEM I, the hydration kinetics are increased with increased heat released observed in the second peak despite clinker dilution. This phenomenon may be related to consumption of water within and around SF particles and its possible uptake by the carbon particles. Reduced dormant period is also visible. However at the end of 72 hours Calorimetry all systems look more or less the same wherein SCP systems using SF shows slightly reduced heat released. The SF particles offer nucleation sites, produce physical packing effect and chemical pozzolanic effect. All these mechanisms work simultaneously as the hydration proceeds and result in improved microstructure which in turn adds to strength and durability against concrete deleterious mechanisms. Safety Concerns The available published data is limited and indicates that silica fume does not pose a health hazard due to its extreme fineness and the nature of silica involved. However caution should be exercised in using this material. The U.S occupational Safety and Health Agency (OSHA) prescribes a permissible exposure limit (PEL) of 15 mg/ m3 of total dust. The American conference of Governmental Industrial Hygienists has established a threshold limit value (TLV) of 10 mg/ m3 of the total dust (9).

Results and Discussion In order to simply get enhanced concrete strength by using SF due to its filler, pozzolanic and nucleation effects, it is unwise to use it in such formulations wherein no attention has been paid to the improvement in the packing density of aggregate phase. After seeing the SEM/TEM and MIP results of SF and carbon particles it may be suggested that antibleed properties may be the result of presence of carbon particles and that of the space between SF agglomerates. Moreover it must be remembered that SF increases early heat release in fresh state of cementitious systems (which is due to cement hydration and SF hydration) so it may not be used in concretes to be poured in hot conditions otherwise the system can crack to do early age cracking etc. There seem to be numerous unknown factors which also contribute to heat buildup and water uptake by SF particles. Silica fume possesses some carbon content which is large irregular particles. Some people suggest that SF particles are hollow circular but it could not be established in this work. It is very seldom that SF particles will be broken. In TEM pictures chains of bigger and smaller particles can be seen. Within the small pores existing between the agglomerates of bigger (primary) and smaller (secondary) interconnected penetrating and inseparable particles, mercury or water can be accommodated .In general water has the tendency to be around the SF particles. In fresh state SF particles hold/uptake some of the mixing water, thereby reducing the

workability and creating slump retention. Usually addition of SF as cement replacement increases the water demand of the cementitious systems incorporating it. In hardened state it improves the strength of the cementitious systems by pore refinement effect.

Concluding Remarks SF should be used with good judgment in HPC/SCC placements especially where aggregate phase has not been packed and especially in hot climates. In order to utilize the full potential of HPC/SCC packing concepts may also be applied to aggregate phase and then binder phase may be packed by SF for optimal response. The increased mercury intrusion and anti-bleed properties of HPC/SCC seem to be due to the presence of carbon particles and to the presence of space within agglomerated SF particle groups. The faster water consumption/uptake is also confirmed in the shrinkage and calorimetric measurements.

Acknowledgements The authors are grateful to the laboratory staff of IKGB, Technical University Freiberg, Germany for their co-operation in carrying out tests. References (1). Rao, G,A., Development of strength with age of mortars containing silica Fume, Cement & Concrtee Research 31( 20010 1141-1146 (2) Temiz, H and Karakeci,A.Y., An investigation on microstructure of cement paste containg fly ash and silica fume, Cement and Concrete Research 32 (2002) 1131-1132 (3) De. Larrard, F, Gorse, J.F and Puch, C., Comparative study of various silica fumes as additives in high-performance cementitious materials, materials & Structures , 1992,25,265-272. (4). Kjellsen, K.O and Atlassi, E.H., Pore structure of cement silica fume systems presence of hollow-shell pores, Cement and Concrete Research 29 (1999) 133-142 5. Rizwan, S.A High Performance Mortars and Concretes Using Secondary Raw Materials- TU Freiberg, Germany, P.hD Thesis, ISBN 978-3-639-17878-4,VDM Verlag Dr.Muller, Germany. 6. Li, Yue., Bao, Junling, and Gou, Yilin., The relationship between Autogenous shrinkage and pore structure of cement paste with mineral admixtures, Construction and Building Materials 24(2010) 1855-1860.

7. Thomas, M.D.A et al., The Effect of supplementary cementitious materials on chloride ion binding in hardened cement paste, Cement and concrete research 42 (2012) 1-7. 8. Rizwan, S.A and Bier, T.A, Self-Compacting Mortars using Various Secondary Raw Materials- ACI Materials Journal, USA, Vol. 106, No. 1, January-February 2009, pp 25-32. (9). Mahotra, V.M., Fly-ash, Slag, Silica Fume and Rice-Husk ash in Concrete: A review, Concrete Internatioanl, Vol 15, April 1993, pp 23-28 10. Schmidt, G.; Schlegel, E.: Mikrosilika Charakterisierung und Rheologie. Keramische Zeitschrift 55 (2003) [11] S.864-69. 11. Schmidt, Gert: Rheologische Charakterisierung von Suspensionen der Calciumsilicathydrat-Synthese. Freiberger Forschungsheft A894 Silikattechnik, Freiberg 2008

APPENDIX

Fig. A SEM Image of SF Particles at 30,000 Magnification Manufacturer data

Table A. A Typical Chemical Data sheet provided by the Manufacturer

Table A (Continued). Chemical Analysis of typical SF as given by the Manufacturer-