(CEMENT and CONCRETE RESEARCH, Vol. 20 pp. 891900, 1990. Pind in he USA. (008.884690. 59,0000. Copyright(c) 1990 Pergamon Press pe THE A.C. RESPONSE OF HARDENED CEMENT PASTE WJ. McCarter feriot-Watt University Department of Civil Engineering Bdinburgh, EHS 4AS Scotland, U.K. R, Brousseau National Research Council of Canada Institute for Research in Construction Materials Section Ottawa, Canada, (Communicued by C.D. Pomeroy) (Received May 21,1990) assTRACT This paper describes an electrical model for cenent and concrete applicable over a wide frequency range and at various stages of hydration. The model contains a non-Debye dispersive elenent to explain the experimental data which are presented. Introduction Some of the first published data on the electrical properties of cement paste can be traced back to the 1930s [1-4]. Since this time, and particularly over the lest decade, there has been a growing interest in the development and use of electrical response techniques as a diagnostic tool in cenent and concrete research [5-15]. Such developments have only come through advances in instrumentation and computer control of data acquisition systens [16]. In many instances, simple resistive models have been used to represent the macroscopic response of cement to an applied alternating electrical field. Ae a consequence, the measurement of resistance (or its reciprocsl, conductance) h been the ain focus of attention of many research vorkers. The teuporal variation of this electricel parameter has been monitored through setting and hardening and attempts have been made to relate its changes to the degree of hydration of the paste [11, 12]. Invariably, electrical measurenents have been carried out at a fixed frequency of electrical field or have been limited to a narrow frequency range. When interpreting data, it has normally been assumed that the resistance measured is due to ionic conduction effects through the wr392 WA. McCaner snd R, Brousseas Vol. 20, No.6 continuous vater-filled capillary cavities within the bulk material. While the pure resistive model is not incorrect, it only gives a partial representation of the physical situation and is only applicable at certain frequencies of applied electrical field. The prime reason for employing an alternating electrical field is to minimize the influence of the electrochemical processes taking place at the electrode/cement interface. The electrode/cement contribution to the total measured impedance is particularly important at lover frequencies and diminishes rapidly the modulating field frequency is increased. Consequently, as far as ionic resistance measurenents are concerned, measurements are normally taken in the range 100Hz ~ 10kHz, primarily to negate these electrode effects. In this paper we aim to develop a more rational approach to electrical measurenents on cement and highlight the importance of frequency on electrical measurements. Data are analysed using complex plane plotting techniques, and a general electrical model is developed for cenent paste. Fauivelent circuit model_snslvsis The impedance behaviour of a material such as hardened cenent paste at angular frequency, w ,can normally be plotted in the complex plane; this allows an equivalent electrical circuit representation to be developed. In trying to design an equivalent electrical circuit which vould correctly model the cement, fone must consider the physical processes and constraints of the systen. Certain rules must be followed in the construction of a model co ensure that the impedance response is correctly simulated, these are: (a) each significant conduction path must be represented by a parallel equivalent path; (>) for simplicity, each region of significance in a path is represented by @ lumped parameter circuit; (c) a parallel combination of resistors and capacitors should also be introduced in the circuit, not only to account for the electrical behaviour at the electrode/cement interface, but also for complex polarisation phenonenon which arise from the paste itself; (4) the ‘resistors’ representing the various conducting processes, and “capacitors”, representing the polarisation proce: have their own composition, microstructural, temperature and frequency dependence; (e) paths of significance are those yielding the least impedance to current flow which results Consider, as an example, a simple parallel combination of a pure resistor and capacitor as shown in Fig.l. The impedance of the circuit can be represented in complex form by the following equation Zl) = 2a) ~ 32"(W) 2 R Row Trtoacd: ~ Teturcy? where = 2xf, £ is the frequency of the applied field, and j =Vol 20.0.6 ELECTRICAL MODEL, AC. RESPONSE, PASTE ww a 32" 4k wry snereasing enn rR z @ CO) Fig. (a) Parallel electrical model, and (b) its impedance plotted in the complex plane. Plotting equation (1) in the complex plane (Argand diagram) vill result in « perfect semi-circle characterised by a single conductivity relexation time t (oR), and the maximum value of -j2" occurs at the characteristic frequency £0 (e1/27t). For most materials, thie ideal respon rarely observed and is more likely to display an inclined semicircle with ite centre, 0, depressed below the real axis by an angle a1/2. This ie displayed in Fig.’ 2. wz Fig. 2: Complex plot shoving a senicircular arc inclined at a1/2. This ‘non-Debye” behaviour, normally associated vith a spread of relaxation times, cannot be described by the classical Debye equations which apply to a single relaxation time. To account for the shape of the inclined complex plot in ionic conductors, a dispersive, frequency-dependent, non-Debye capacitance Cu) has been proposed [17-19]. The non-Debye capacitance is given by the r8tation: @ c,t) = ecse)™ og vhere, 2 = Ina anda is defined above, C is a constant and equal to the equivalent circuit capacitance. Hence, for a parallel combination of frequency independent resistance, R and non-Debye capacitance (Fig. 3), the impedance Z(w) is given by: @ aw = Bec)?tes WJ. McCarter and R, Browseas Vol. 20, No.6 Glu 4 rn Ge Fig. 3: Effective parallel resistance R and non-Debye capacitance C,(w). ‘AS. representation of cement paste The low frequency response of cement paste is uoruslly represented by the circuit shove in Pig. S(a). AC frequencies close to duc. electrofe affects would be operative.” This can be represented as a. parallel coubination of Feelator, Ares and capscitor yy ~ this ie the charge cranster resistance and double layer itance (respectively) at the electrode/cement paste interface. Flenent Ry represents the bulk fone vevistance of the cenent paste wiieh is Independedt of the applied frequency of electrical field. The impedance 2(u) of the lumped systen is given by: 2 seeeeeee (6) 2) = R, + (——t a Tey ae the frequency increases the second term on the right hand side of equation (6) decreases, and at sone frequency (as yet undetermined), 2(u)=R, measured inpedance would be equal to the bulk ionic resistance of the This nodel would imply that vhen electrode processes are effectively el the resistance vould renain constant vith increasing frequeacy (See Fig. 4(b)). However, this is not the case, and even at frequencies in excess of 10kiz (i.e. where electrode effects vould be considered “elininated”) the impedance still displays a frequency dependence (20, 21]. This necessitates the introduction of another conduction path in accordance vith the rules already described, in Fig. 4: (a) Low frequency representation of cement paste, and (b) complex impedance response for this circuit.Vol. 20, No.6 ELECTRICAL MODEL, AC. RESPONSE, PASTE. 5 parallel vith the frequency-independent ionic resistance &,. Fig. 5(a) displays @ wodel to account for such # response and includée a “aon-Debye” capacitance; R, has been included to account for the fact that the complex plot does not pase through the origin at high frequencies. The theoretical response of such amodel is given in Fig. 5(d). Lolly T o Re @ bulk=—— electrode ve fe f 4 i o Fig. 5: (a) Electrical model for cenent and, (b) the complex impedance response of this model. For completeness, a Warburg (or Faradic) impedance element, W, is included in the response to account for slow ionic diffusion effects at the electrode/cenent interface at ultra jlow frequencies. Tt is characterised by a low frequency spur inclined at 45°. In this model, ct) = 6 Ge™ , my = tay and, see OD Capo) = 2630)? , ng = Lag where C, and C, are the equivalent (parallel) circuit bulk capacitance and double Tayer caphcitance respectively. The existance and/or prominence of the arcs will depend on ionic mobility and charge concentration, hence degree of hydration of the cement paste.96 WI. McCarran R. Browsseas Vol. 20,No.6 Methods For the current test programe, a Solatron 1260 frequency response analyser vas used to obtain complex impedance data over the frequency range l0niiz-15¥iz. The analyser vas interfaced to a Hevlett Packard HP9836U microcomputer, a HP plotter and HP printer, enabling data to be obtained in both graphical and hard copy formats. A logarithmic eveep technique was used and complex impedance measurenents taken at 150 spot frequencies vithin the above limits. A signal amplitude of 1.0 Volts was used throughout the sveep and incoming data vere automatically “nulled” at every spot frequency for stray, open and short circuit residuals. Ordinary Portland cement (ASTM Type 1) vas used and samples (50x50x50mn) were gauged to give a vater-cenent ratio of 0.27 (by veight). Stainless steel electrodes (Type 304) were embedded within the specimens and, on demoulding, werg sealed with a latex paint. Specimens vere left in a laboratory atmosphere (22%c, 552RH). Presentation and discussion of results Couplex data were taken at 1 da; wnd 100 days after gauging and are presented in Fige.6 and 7. Fig.6 displays che complete couplex impedance response for the frequency range 10nHz-15Miz, while Fig.7 presents an enlargenent of the high frequency arc at 1 day (Fig.7(a)), 10 days (Fig.7(b)) and 100 days (Fig.7(c)) after gauging. Fron the data presented in Fig.6 it is evident that two, well developed, arcs exist, one in the high frequency region and the other in the low frequency region ~ although the frequency range over vhich they persist changes vith tine of hydration, The low-frequency arc represents the electrode-cenent interface effects, whereas bulk effects are represented by the high-frequency arc. From Fig.6 it would appear that the complex plot is dominated by electrode-cenent interface effects; only when plotted at an enlarged scale (Fig.7) does the high-frequency are become apparent. In all cases, the centre of the arc is depressed below the real (resistance) axis indicating the Jonscher model discussed earlier ie equally applicable to cement pas From the projected intercepts of the arcs with the real axis (see also Fig.5), various values can be obtained most notably the ionic resistance, R,, and charge transfer resistance, R.. These are tabulated in Table 1. As expected, as hydration proceeds, these values increase. An interesting feature of these curves is that the frequency (f,) at which the bulk ionic-resistance of the sample can be obtained is dependent upon the degree of hydration of the paste. Table 1: Variation in electrical parameters vith increa degree of hydration Ry Ree f fe f3 Days Hydration i nct Be a a2 1 137.25 5.95 3Mel 8.17 0.17 O12 10 552 13.8 4.82 20.3 2.28 0.22 0.10 100 2000 43.3 2.73 ao 1.49 0.29 OldVol. 20, No. 6 ELECTRICAL MODEL, AC. RESPONSE, PASTE. 7 This frequency decreases with increasing hydration tine. The characteristic Erequency of the high and low frequency arcs, f, and f, (respectively), which occurs at the peak ~jZ , decrease with increasing timé of hydration. | Once again, this is due to the reduction charge mobility due to gel grovth and pore constriction. The dispersion parameter, ©), increases by, approximately 70% over the test period whereas e, only showela slight variation with no general trend evident. At the lowfreqiency end of the complex plot, and particularly at 1 day hydration, an inductive back-loop is evident (Fig.5). This could signify the formation of a thin oxide layer at the cement-electrode interface, caused possibly by reaction betveen the alkalis in the cement paste and the stainless steel. The influence of this layer becomes less significant with increasing frequency and increasing degree of hydration. For the current testing programme, coaxial, screened leads connected the sample to the frequency response analyser using a patent, in-circuit test module (Part Wo.12603A). Tt should be emphasised that data became increasingly degraded at the higher frequencies due to lead inductive effects; this is apparant vhen the imaginary component of impedance turns positive, is essential to eliminate this spurious effect from the incoming di “pulling” procedure described earlier. Tt was found fron preliminary studies that for frequencies in excess of about 251lz inductive effects doninated the measured impedance even after carrying out the “nulling” proces Hence restricting the upper frequency limit to 1SMiz. To obtain data at frequencies >25Miz, screened Leads would give meaningless results and a more complex testing arrangement vould be required. 2eaae — \e0a0 IHRGINARY (ohms) @ e00 7 08 Tseee e080 REAL (onme) Fig. 6: Development of complex impedance over test period.os IWAGINARY (ohms) IMAGINARY Cohes? 300 20a 198 502 (WJ, MeCarier and R, Brousseau orer i 1eo 202 302 REAL (ohne) -—————————— (10a Ld e 302 eee. REAL (ohne) Vol. 20,No.6Vol. 20, No. § ELECTRICAL MODEL, A.C. RESPONSE, PASTE 39 2000 zoe | i (0100 ane = se0e} a , 2 vee ze08 seve REAL (ones) Fig. 7: Enlargement of high-frequency arc. Sonclusions and concluding comments This paper describes an electrical model for hardened cenent paste applicable over a vide frequency spectrum and typical resulte are presented. Complex two distinct regions - one relating to electrode-cenent interface proce: the other due to bulk processes. Several immittance parameters vere introduced and their variation with tine of hydration is presented, The study hae shown that the electrical properties of cement based materials are frequency dependent and vide-band frequency scans are essential for correct interpretation of results, The following conclusions can be dravn fron this study: @) hydration proceeds, the radii of the complex arcs increase; (b) the complex arcs fora the ri art of a semi-circle whose centre is depressed below axis. This can be explained by the introduction of a non-Debye itive elenent into the equivalent circuit; (c) the frequency (£3) at which the low-frequency are “turns-over” into the high-frequency ave, and the characteristic frequency (f,) decrease vith increasing degree of hydration; (4) screened leads vere found adequate up to 15i#iz, although calibration routines were essential to obtain sample impedances.900) WJ. MeCaner and R.Brouseas Vol. 20, No.6 Acknovledzenente The authors wish to thank Professor P.W. Jowitt, Read of Department of Civil engineering, Heriot-Watt University and the National Research Council of Canada for placing their facilities at the authors’ dispo Dr W.J. McCarter acknowledges the receipt of a research grant fron the Science and Engineering Research Council (GR/F 26645). References 1, Petin, N., Kigerovitsch, M. and Gajsinovitsch, E. Jrnl. of Gen, Chen. of U.8.8.8., Vol.2, 1932, pp 614-629. Dorsch, K.E. Cement and Concrete Manufacture, Vol.6, No.4, April 1933, pp 131-142. 3. Michelsen, 8. Zement, Vol.22, No.3, 17 Aug. 1933, pp 457-461. 4. Kind, V.A. and Zhuraler, V.P. Teenent, Vol.5, No.9, 1937, pp 21-26. Calleja, J. Jeni. Aner. Coner. Inst., 23, 1952, pp 525-536. 6. Warmond, E. and Robson, T.D. The Engineer, Vol.199,'21 Jan. 1955, pp 78-80. 7. Ten. Ibid, Vol.199, 28 Jan. 1955, pp 114-115. 8. Whittington, H.W., McCarter, W.J. and Forde, M.C, Mag. Conc. Res., Vol.33, No.114, March 1981, pp 48-60. 9. Tamas, F.D. Cem. and Concer. Res., Vol.12, No.1, 1982, pp 115-120. 10. Hansson, 1.L.H, and Hansson, C.M. Ibid, Vol.13, 1983, pp 675-683, 11, Hughes, B.P., Soleit, A.K.0. and Brierly, R.W. Mag. Concer. Res., Vol.37, No.133, 1985, pp 263-248, 12. Morelli, 8. PhD Thesis, University of Edinburgh, 1985, p 179. 13. Buenfield, N. and Newnan, J.B. Mag. Concr. Res., Vol.36, No.67, 1984, pp 1s, Tamas, F.D., Farkas, E., Yoros, M. and Roy, D.M. Gen. and Concr. Res., Yol.17, No.2, 1987, pp 340-348. 15. McCarter, W.J. and Afshar, A.B. Jeni, Matl. Science, No.23, 1988, pp 488-496. 16. Iden. ASCE (Technical Council on Computer Practices), Vol.1, No.1, Jan. 1987, pp 50-60. 17. Jonscher, A.K. Nature, Yol.253, Feb. 27 1975, pp 717-719. 18. Tden. Tbid, Vol.267, June 23 1977, pp 675-679. 19. Tdem. Jenl. Matl. Science, Vol-13, 1978, pp 553-562. 20. MeCarter, W.J., Bouzid, N. and Garvin, 8. Jenl. Matl. Science Letters, 7, 1988, pp 1056-1047 21, MeCarter, W.J. Cem. Conc. Res., Vol-17, No.1, 1987, pp 55-64.