Uitrasonie Spectroscopic Investigation of the Structural and Mechanical Evolutions of a Reactive Powder Concrete by V. Morin, F. Cohen Tenoudji, CC. Vemet, A. Feylessouti and P. Ric ‘Svpnopsis: The ultrsonie wave propagation is a nondestructive method particularly wellsuited to monitor the evolution of the structuration of @ Reactive Powder Concrete. Each stage of the structural mechamsm can be brought out withthe use of longitudinal and transverse waves both in reflection and transmission modes. ‘The ultrasonic set-up is composed of a tes-cell filled with concrete, equipped ‘with broad band transducers of frequency range centered at 400 kHz. The cell is immersed in an isothermal bath regulated at 20° C and the ultrasonic signals rded with a period of one or ten minutes, are analyzed in the time and frequency domains. Furthermore, an isothermal calorimetric measurement is used to evaluate the hydration degree of the conerete and then to represent the ultrasonic results as function of time or hydration degree alpha, The ultrasonic and calorimetric measurements are simultaneously performed duriny three days The correlation of the informations trom these different techniques provides an cesier interpretation and a better understanding of the different stages of the structuration of the Reactive Powder Concrete Keywords’ cement, concrete, eactive powder concrete, ultrasonic spectroscopy, elastic modulus, reflection coetficient, hydration degree Shabate 1998 “19.V. Morin is junior researcher in LUAP ; this work is part of his Ph, D. thesis which will be defended at Paris VII University F. Cohen Tenoudii is professor at Paris VIl University ; he is specialised in the control of materials with ultrasonics and in signal analysis. CC. Vernet isthe director of the Concrete Laboratory ofthe Scientific Direction of Bouygues BTP ; he isa specialist ofthe chemistry of cement-based materials A. Feylessoufi was a scientific advisor in the Scientific Direction of Bouygues Group ; his research field is the mechanical behaviour of heterogeneous materials P. Richard was the scientific director and vice-president of Bouygues Group ; he initiated the research and development of Reactive Powder Concrete, INTRODUCTION ‘Tre longterm properties of cement based materials are conditionned by the kinetic of the stucturation during the sering period. Cohen Tenoudji and Vernet have demonstrated the interest of Ultrasonic Spectroscopy inthe study of cement hydration mechanisms (1), This new muliffequency approach adds the Possibility to evaluate the dynamic properties of the material at different scales by the frequency dependence of its reflection and tansssion responses tothe ultrasonic slitation. In this article, this approach has been extended to composite materials as Reactive Powder Concrete. In these material, the large amount of information Provided by this technique seems to decipher the complexity of the successive ‘Bhenomens volved in their evolution during the early age of maturation. Former studies on concrete with ultrasonic method (1-5), have shown that this technique is well-suited to stdy the evolution of tis matva fom the mixing > the end ofthe setting. During this time, the cement paste goes through large sodifcaion nits stucturation. Just ar the mixing, the cement is smula to ‘highly concentrated suspension of solid particles in water. As soon as hydration reaction begins, the hydration products develop progressive connection between the particles which confers an increasing rigidity to the cement paste which can be monitored by ultrasonics. “Two different modes of ultrasonic investigation can be used: transmission and reflectomety. The transmission mode provides the ultrasonic velocity and attenuation of longitudinal and transverse waves through the specimen. In the reflection mode, the signals reflected atthe interface between the cell wall and the paste are monitored. Even when during the first hours after mixing no signals can be transmitted through the paste, with the echographic mode early informations about the structuration of the medium can be obtained. Indeed at this stage, the ultrasonic waves (longitudinal or transverse) penetrate into a small “120-layer in the cement paste before being reflected and they bring beck an information on the state of the paste MATERIALS AND EQUIPMENT Specimen description The Reactive Powder Concrete used in this study has the following ‘components expressed with their respective mass to cement ratios : sand (1.43), silica fame (0.325), crushed quartz (0.3), polyacrylate superplastcizer (0.018) and water (0.2) Tye different dry powders are firstly mixed during 3 minutes, then the water and. the superplaticizer are added and mixed during 3 to $ minutes. Time zero is ‘chosen as the instant when water is added to the powders. Airis removed from the paste with a regular laboratory running water-air pump. The specimen mass im the ultrasonic cel is about 0.7 kg witha specific gravity of 2.4 Ultrasonic Set-up ‘The ultrasonic pulser-receiver conceived and built at LUAP laboratory, performs in both transmission and echogrephic modes. All the settings : the frequency range, the typeof excitation of transducers, the peak voltae, and the amplifies gains are computer controlled. A digitizing board in the computer of sampling frequency 64 MHz, allows the use of a Virtual Oscilloscope program with which the whole set of measurements (up to 32 different ultrasonic signals with their own settings) can be scheduled for several days. A second program. Performs the analysis of the recorded signals in the time and frequency domains ‘The treatment ofthe recorded signals in the Fourier domain gives the ability to perform the spectroscopic analysis of the properties of the material at a particular frequency ; furthermore, it provides beter accuracy in time ‘measurements (Ins). A graphic user interface allows an easy selection of the pants of the signal to be analyzed and their automated treatments and this in experiments which can deal with several hundred of waveforms. ‘The broad band transducers with a central frequency of 400 kiiz are excited by a very short voltage-pulse (1-2ys). The transducers are fixed on the walls of the test-cell shaped as a flat cylinder with a radius of 65 mm and a ‘thickness of 30 mm. After thorough mixing and degassing, the concrete paste is Poured into the cell which is then immersed in a bath regulated at 20 °C within £002, aieCalorimetric monitoring Simultaneously with the ultrsonic measurements, isothermal calorimetric measurements were made in order to calculate the hydration degree ofthe concrete specimen. The measurement ofthe released heat, with the use of the hydration enthalpy of the different constituents, leads to the hydration degree (ato ofthe heat produced ata given time tothe heat that would be produced if all cement had been hydrated) from which we can infer the amount of hydrates, formed. We can then analyze the kinetic of evolution of the mechanical Properties as given by ultrasonic spectroscopy, either in relation with time or ‘with the amounts of reacted metter. The calorimetric results of this Reactive Powder Concrete are given in Figure 1. The hydration degree a has been calculated by using a complete hydration released heat value Qinax = 483 Joules by gramm of cement. The zero of hydration degre is taken at hour 10 where the carly dissipated power passes by a minimum. The peak of dissipated power ‘occurs at 35 hours, This relatively large time is a secondary effect caused by the important amount of superplasticizer (1.8% mass proportion) used in this RPC formulation. RESULTS AND DISCUSSION In RPC samples which have very low water contents we measure very small longitudinal velocities (< 300 mis) at early ages, Ths isto be compared to values inthe order of 1500 mis measured i concretes with higher water contents (w/e > 0.3 [4]. This expresses the fact that even ifthe superplasicizer gives a ‘very fluid consistency tothe RPC after mixing, the mechanical coupling between solid particles is weak. This mechanical coupling is provided by water in ‘concrete leading to the higher initial velocities. In RBC, velocities generally vary ftom very small values (< 300 mis) to larger ones : 3000 ru for shear waves oF 4500 mvs for longitudinal waves, characterizing the hardening ofthe materials The properties of transmiting the ulasonic waves ofthe setting medium are principally those of a low-pas filter until itis fully connected. The cut-off frequency of the filter inreases with the hydration degree. In Figure 2a and 2b the evolution versus time and hydration degree of the transverse amplitude ‘measured in transmission at several frequencies (100 to 600 kHz) is represented. In this frequency range it is not possible to detect any signal until 26 hours after mixing. The 100 iz frequency component appears fist and is followed by the apparition of spectral components of higher and higher frequencies. In figure 2 itis seen that although the medium is getting it rigidity at 100 kilz at 3% of hydration degre, it does not get srength at 600 KFz until a degree of hydration of $%, The degrees of hydration when the spectral components emerge from background noise are plotted in figure 3. The increase of this initial degree of “t22-hydration with frequency expresies the fict that asthe rection goes on clusters of diminishing average sizes remain to be connected. Ths increase of connections number induces the enlargement of the rigidity of the medium. Its seen that the transverse waves are very sensitive tothe solid structration of the paste, Indeed, if transverse wave ean be transmitted through the specimen, i ‘means that the medium is connected enough o cary tis wave Ifa percolation description ofthe early evolution of the shear clastic modulus @ is used, its variation with time should be given by a power law (4-5) G= a(t" where fi a characteristic time which represents the instant ofthe percolation of ‘the bounds and is the exponent of this critical phenomenon. By applying a logarithmic regresion inthe ist hous of the evolution of the shear modulus, the time when the medium reaches a transverse elasticity can be evaluated by extrapolation. This point may be identified as a percolation ‘bound point (PB). In tis RPC formula we obtain using the frequency component of signals at 40 kHz: 1,=21 hours and y = 3.13. The value of 3.13 is higher than the values in the range of 1.9-2.2 found for cement pastes and mortars [4-5] with much higher wie ratios The shorter distance between solid particles in RPC makes the evolution faster with the amount of formation of hydrates (at a= 1.5% onl). If the evolution of the modulus ofthe transverse reflection coefficient in finetion of time and hydration degree is observed in Figures 4a and 4b, its seem tha the ‘medium approximativey atthe same time t = & becomes very dispersive. AS already seen fom transmission measurements, the medium doesn't behave rmechanically inthe same manner at different frequencies. At this stage, the medium favors a better propagation ofthe low fecuencies tat of higher ones resulting in a lower reflection coefficient. It is thought that at this time, transverse waves become sensitive to the size of the connected particles of clusters, This dispersive effect disappears at 33 hours. Then, tis thought tha, at t= 33 hours, the hydration reactions entail the formation of a large solid skeleton ‘hich takes up the whole volume ofthe specimen, although some litle petles Inside this skeleton could remain unconnected CONCLUDING REMARKS We have showm in this anicle that the spectroscopic ultrasonic methodology presented here is a very powerful technique to monitor the evolution of the structuration and the mechanical properties of cement based ‘materials. Both reflection and transmission modes have been shown to be very ie:sensitive to the connection process at different scales. We have observed the low early acoustic velocities characteristic of highly concentrated suspensions. The spectroscopic analysis has shown the progressive structuration of the material Which begins at very low hydration degree (~ 2%). Due to the larger compacity ‘of RPC, the percolation coefficient of their increasing elastic shear modulus is ‘higher than that of cements with higher water to cement ratios. From a practical point of view, this method is easy to implement and is able to be a part of an intervention process upon the setting dynamic and the improvement of ultimate mechanical behaviour ofthese materials REFERENCES 1. LevassortF., Cohen Tenouaii F., and Vernet C., in Rapport de DEA. Acoustique Physique, Université Paris VII, Paris 1991 2. Byfors J., Pulse velocity measurements for indicating ofthe compressive strength at early ages, Cementa AB, Sweden, 1980. 3, Sayers CM. and Dahlin A., Propagation of ultrasound through hydrating cement pastes at early times, Advn Cem Bas Mat, 1, 12-21, 1993. 4, Boumiz A., Vernet C. and Cohen Tenousii F., Mechanical properties of ‘cement pastes and mortars at early ages , Advn Cem Bas Mat, 3, 94-106, 1996, 5, Morin, V., Cohen Tenoudji F, Vernet C., Study of the viscoelastic behaviour cof cement pastes at early ages with ultrasonic waves in echographic mode, ‘Second RILEM Workshop on Hydration and Setting, Dijon, France, 1997. Prabe 1996 a4gue ele i Ba Bo os fos i dos ° low 0 5 was 0 25 39 35 a 45 BD 45 60 OS Ser wave Spat Ample aon 3 on ow on DS Pe Fm) HTT dey THT pelt aa hf Vain! : Rotation epee Fig. 2. Transmitted shear wave amplitude function of time (2a) and hydration degree (2b) at different frequencies age 1998su 400 soo 6007 Preaueny Fig. 3, Degree of hydration of firsily detected transmitted signal at different frequencies. os 1% % 2 30 3s w0 “Tine Cours) i z # hk "yuan dare Fig. 4. Shear wave reflection coefficient modulus function of time (4a) and hydration degree (4) at different frequencies,