Colloids and Surfaces A: Physicochemical and Engineering Aspects 161 (2000) 401 415 www.elsevier.

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Surface energetics of calcium carbonates using inverse gas chromatography

D. Steven Keller *, Philip Luner
Empire State Paper Research Institute, State Uni6ersity of New York, College of En6ironmental Science and Forestry, Syracuse, NY 13210, USA Received 4 November 1998; accepted 19 April 1999

Abstract Various calcium carbonate samples were characterized by inverse gas chromatography (IGC) at innite dilution. The interactions between the samples and hydrocarbon probes, C5 C10 were related to the retention volume in gas chromatographic experiments. The surface energetics of chalk, marble and precipitated calcium carbonate (PCC) were determined in terms of the apolar component of the surface free energy k LW and the differential enthalpy of S adsorption, DH $ . These results were evaluated with respect to bulk chemical composition, BET surface area and A pore structure. The results suggest that physi- and chemisorbed water bound at surface sites and within the pore structure signicantly inuence the surface properties of the calcium carbonates. The values of k LW and H $ after S A redeposition of the water adlayer suggested reversibility of the water sorption process and the resulting changes in the energetics of the surfaces. Values of k LW for the chalk samples in the initial state were 140 180 mJ m 2, whereas the S marble and PCC were : 55mJ m 2. Removal of bound and pore water by heating at elevated temperatures caused a progressive increase in the k LW to :250 mJ m 2 for the PCC sample. The k LW of the chalk sample also increased S S but to a much lesser extent. H $ values for the samples followed the trend chalk\marble \ PCC. 2000 Elsevier A Science B.V. All rights reserved.
Keywords: Adsorption; Alkane; Calcite; Calcium carbonate; Chalk; Enthalpy; Inverse gas chromatography; Surface free energy; Thermodynamics; Water

1. Introduction The industrial importance of calcium carbonate (CaCO3) as a ller in composite materials such as plastics and paper is well recognized. As a result,
 This article was originally submitted to the Per Stenius Special issue. * Corresponding author. Tel.: + 1-315-4706907; fax: + 1315-4706945. E-mail address: dskeller@esf.edu (D. Steven Keller)

characterization of the surface energetics is critical in developing an understanding of the forces of interaction between ller and substrate. Several investigators have examined the modication of the surface properties of CaCO3 through the use of surface grafted compounds in order to improve particle cohesion [14],. The typical physical characteristics of ller particles, i.e. ne particle size and irregular shape, precludes the use of more classical methods of surface chemical analysis used on large planer surfaces such as contact

0927-7757/00/$ - see front matter 2000 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 7 - 7 7 5 7 ( 9 9 ) 0 0 2 1 2 - 5

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angle measurements and Wilhelmy plate experiments to obtain reliable surface energetic information. The surface energetics of CaCO3 has been studied using contact angle on cleaved crystals [5,6] and aggregated powders [7], although the relevance of these results to the ne particle surface may be questioned. Other methods have also been used such as immersion calorimetry [8 10] and spectroscopic methods [11]. A general discussion of the subject was given by Sanders [12]. A more direct approach to the characterization of the surface chemistry of ne particle calcium carbonates has been to study the adsorption isotherms of water vapor [13 17]. Inverse gas chromatography (IGC) is a method that was developed to determine the surface energetics of ne powders and liquids by measuring the dynamic adsorption characteristics of probe gases [18]. The convenience of experimentation and control of test conditions has inspired the recent interest in applying IGC for the analysis of ller/pigments such as CaCO3 [19 21]. The effects of treatment of bers and calcium carbonates with alkylketene dimer has also been examined [22,23]. An estimate of the dispersive (London) component of the surface free energy, k d, may be deterS mined by measuring the interaction of linear alkane probe gases with the surface. Polar gaseous probes are used to determine the specic interaction parameters from which the relative acidity and basicity of the surface can be established [18,2225]. Papirer et al. [2,3] utilized IGC in their investigation of precipitated calcium carbonate (PCC) and the effect of surface coverage with stearic acid on the surface properties. They determined the dispersive component of the surface free energy, k d, of untreated CaCO3 at 90C to be 50.5 S mJm 2 and H $ for alkanes C5 C8 to range A from 9 to 17 kJ mol 1. Ahsan et al. [3] found H $ to range from 6.4 to 52.6 kJ mol 1 in A their work with PCC using C6 C8. Ahsan suggested that the discrepancy could be explained by differences in sample preparation or the conditioning of the carrier gas. IGC has also been used to examine the interaction of polar probes with CaCO3 to determine specic interactions, and the acid/base activity of the surface [3,26].

The aim of this investigation was to utilize IGC to determine the gas/solid surface energetics of several calcium carbonates and observe the effect of sample origin. The specic objectives were to characterize the interactions of alkanes with PCC, ground marble, and ground chalk using IGC at innite dilution. The method facilitates the determination of the apolar component of the surface free energy, k LW, and the enthalpy of adsorption, S H $ , of the alkanes. The sensitivity of the IGC A method to detect differences in the different samples was also evaluated.

2. Experimental

2.1. Materials
Four samples of commercially available calcium carbonate were examined in this investigation. The rst was a synthetic PCC, Albacar 5970 by Specialty Minerals Inc. A ground marble that was mined in Alabama was supplied by ECC America Inc. as Atomite. Two samples, identied as chalk I and chalk II, were acquired from different sources. The chalk I sample was supplied by Omya, Inc. from Germany. Chalk II was a mined sample from Dover, England received in nugget form from Ward Natural Science Est. as product no. 46E1445, 46E1447, 46E1449, and hand-ground to size immediately prior to analysis. Particle shapes were examined using scanning electron microscopy. The PCC particles appeared to be well-formed scalenahedrals as illustrated in g. 1(a). The ground marble particles were observed to have rhombohedral form, cf. g. 1(b), although an increased amount of irregularity is evident. For the two chalk samples, cf. g. 1(c), (d), discrete particles appear rhombohedral and clusters of coccoliths are clearly visible. The bulk phase crystal structure of the samples was examined using an infrared spectroscopic technique [27] where the dominant structure in all samples was found to be calcite. The particle size distribution of the samples were determined using a Sedigraph 5500L (Micromeritics) particle size analyzer. The results, expressed as apparent spherical diameter, are pro-

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Fig. 1. Scanning electron micrograph of calcium carbonate samples. (a) Precipitated calcium carbonate; (b) ground marble; (c) mined chalk; and (d) hand ground chalk.

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Table 1 Physical characteristics Particle diameter Sample Median (mm) 2.4 3.0 3.2 Maximum (mm) 4.5 12 15 Specic surface area Initial state (m2 g1) 9.0 2.9 2.1 Outgassed at 200C (m2 g1) 10.2 3.2 2.1 Mercury porosimetry Pore volume (cc1 g1) 0.97 0.41 0.35 Pore diameter (mm) 1.10 0.60 0.90

PCC Marble Chalk I

vided in Table 1. Because of the small particle sizes, all samples required preparation to improve gas permeability in chromatographic columns to provide acceptable pressure drops. This involved the formation of pellets by compression of the powders to 15 kpsi in a hydraulic press. Pellets were then ground and sieved to obtain a 250 400 mm size fraction which was used to pack the gas chromatographic columns. A scanning electron micrograph of aggregated PCC is shown in Fig. 2. Aggregation of the particles by this procedure was found to have no affect on the measured specic surface area and permitted the analysis of micron size particles without having excessively high-pressure differential across the chromatographic column. The specic surface areas of the samples were determined using a multipoint BET method with nitrogen as the adsorbate in a Quantasorb Sorption System (Quantachrome). Pore volume analysis was performed on the PCC and chalk I samples using an ASAP 2000 (Micromeritics). The pore volume distributions were calculated using the BJH method [28,29]. Both samples were analyzed in two states. The rst analysis was conducted without outgassing of the adsorbed water to obtain information on the pore size distribution of the samples in the initial state. The samples were then examined following outgassing at 200C for 24 h, which was similar to the exposure conditions used in IGC analyses. The results of all surface analyses are shown in Table 1. Bulk phase elemental analysis was conducted on the samples using inductive coupled argon plasma/atomic emission spectroscopy, ICP/AES using an FMA-03 (Spectro Analytical Instruments). The results are provided in Table 2 as oxide equivalents.

IGC experiments were conducted using a HP 5890 Series II gas chromatograph (Hewlett-Packard) equipped with a ame ionization detector. The instrument was directly interfaced to a PC computer for system control and acquisition of chromatograms. Stainless steel columns with a diameter of 5.34 mm and a length of 60.0 cm were packed with approximately 10 g of aggregated CaCO3 particles. Preconditioning of the columns was carried with the columns in the gas chromatograph. High purity nitrogen (99.999%) that had been passed through two moisture/oxygen traps was used as the carrier gas. The ow rate of the N2 was controlled at 20.59 0.1 ml min 1. Reagent grade alkanes, C5 C10 were used as test

Fig. 2. Scanning electron micrograph of precipitated calcium carbonate (PCC) aggregates prepared by compression for use in inverse gas chromatography (IGC) column packing.

D. Ste6en Keller, P. Luner / Colloids and Surfaces A: Physicochem. Eng. Aspects 161 (2000) 401415 Table 2 Trace chemical composition in wt% oxide equivalent Sample PCC Marble Chalk I Chalk II MgO 0.26 0.55 0.26 0.20 SiO2 0.06 0.64 3.16 0.44 Na2O 0.21 0.19 0.31 0.26 Fe2O3 0.05 0.06 0.14 0.07 MnO2 .04 .04

405

probes. Methane was used as the non-interacting reference marker to determine the dead volume of the column. Chromatograms were recorded for each probe. All calculations were conducted using the rst moment of the peak as the retention time and symmetry of the peak was veried by comparison of these results with the time at peak maximum. Two approaches were taken in the examination of the CaCO3 samples using IGC analysis. The rst, referred to as sequential isothermal analysis, involved monitoring changes in V at different s intervals up to 150 h as the sample was held at a constant temperature under a :20 ml min 1 N2 purge. New columns were prepared for each temperature (60, 100, or 140C). The second experimental approach, referred to as preconditioned analysis, involved the outgassing of the column at specied elevated temperatures, Tp, before IGC analysis [3,22,30]. The effect of preconditioning temperature was examined because general agreement on an ideal pretreatment temperature for CaCO3 did not exist. Therefore, samples were conditioned at Tp =100, 200, or 300C for 24 h prior to IGC analysis. The retention times of the alkane probes were then determined at Tp and at several lower temperatures to determine k LW and S H $ . A

quired to completely elute the adsorbate, less the dead volume of the column, per unit mass or surface area of adsorbent. Many of the earlier studies in IGC, especially with polymers, involved the analysis across the gas/liquid interface where it was useful to express the specic retention volume in terms of adsorbent mass, V . However, g for the analysis of solid surfaces, as in the present study, expression in terms of specic surface area,V , is more appropriate. S The mass and area specic retention volumes are related to the retention time, t, of injected probes and the specic surface area, Asp, by the relationship [31] Vo= S V o jFcol(tp tm) g = Asp Aspw (1)

The subscripts p and m identify the retention times of the probe and a non-interacting marker, respectively. The parameter w is the weight of adsorbent in the column, j represents the James Martin correction for compressibility, and Fcol is the ow rate of carrier gas within the column that has been corrected for column temperature. A more detailed discussion of experimental parameters is given elsewhere [20,23]. The partition coefcient or Henrys law constant, KS, may be expressed as [32]: KS = lim
c0

 
lG lc

(2)

A, T

where c is the molar concentration of the adsorbate in the gas phase and G is the molar concentration per unit surface area of the adsorbent, assuming constant surface area, A, and temperature, T. For analysis at innite dilution, (or zero coverage), Eq. (2) becomes the simple ratio of G/c and may take the form: Vo= S Vo K g = S Asp RTC (3)

2.2. IGC theory

Calculation of the thermodynamics of adsorption from IGC analysis is based on the determination of the specic retention volume, V, of a known adsorbate probe as it passes through a chromatographic column containing the adsorbent under examination. The specic retention volume represents the volume of carrier gas re-

where R is the gas constant and TC is the column temperature. The differential enthalpy of adsorption, H o , A may be determined by measuring values for V o at S different column temperatures and applying the relationship [31]:

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d(lnV o) S H o = R A d(T 1) C

(4)

is obtained graphically from the slope of the plot of RlnV versus 1/TC. s The standard molar free energy of adsorption, G o , of the probe on the adsorbent is related A to the Henrys law constant by the relationship KSpsg = RTlnV o +C G o = RTln A S ys

 

equation for the work of adhesion of a non-polar liquid and a surface in terms of the incremental change in free energy per methylene group, G CH2. Values for G CH2 are accessed A A from the difference in G o for adjacent memA bers of a homologous series of linear alkanes from the relationship: G CH2 = RTln A

(5)

 

K n+1 V n+1 S S = RTln Kn Vn S S

 

(7) G CH2values are determined graphically as the A slope of a plot of V o versus the number of carS bons in the alkane, n. The equation that Dorris and Gray [31] derived may be rearranged to solve for k d so that S kd= S 1 kCH2

Here a standard reference gas pressure, psg, and the spreading pressure, ys, are dened by the chosen reference state [33,34]. The integration constant, C, is a function of these parameters and may be assumed constant for a given adsorbent and a homologous series of probes. When non-polar molecules, such as n-alkanes are used as probe gases in IGC, the energetics of adsorption are considered non-coulombic and result entirely from Lifshitz van der Waals (LW) interactions. The LW contributions to the surface free energy, k LW, encompasses the elecS tromagnetic interactions including the dispersive (London), k d, induction (Debye), k iS, and orienS tation (Keesom), k v, components so that: S k LW = k d + k iS +k v S S S (6)

G CH2 A 2Na

(8)

In the case of IGC experiments conducted at innite dilution of the gaseous probe, the pairwise-addition approximation [35] provides a means to interpret the signicance each separate component to the overall LW interaction. The assumption in this case is that intermolecular distances between probe molecules are large and the Debye and Keesom components are not suppressed by neighboring molecules as in condensed phase-condensed phase interactions, e.g. liquid/solid or solid/solid. The impact of this perspective on existing theory for the determination of k d by IGC, and experimental evidence S for the signicant effect that surface polarity has on the apolar interactions that occur in IGC are given in this section. A method for estimating the London-dispersive component of surface free energy, k d, from S IGC data was proposed Dorris and Gray [31]. Their approach involved the use of Fowkes [36]

where N is Avogadros number, a is the cross , sectional area of the methylene group (6A2) and kCH2is the surface energy of a solid consisting of only -CH2- groups, i.e. polyethylene. Since the interactions of the alkanes with the surface will involve all of LW interactions, the solution to Eq. (8) is more appropriately given as k LW [37]. Furthermore, because the probes S are in the dilute gaseous state, the Debye induction interactions, k iS, that result from dipoles induced in the alkane molecules by the electric elds at the adsorbent surface may be considerable [35], especially for high energy materials such as mineral llers [38]. Dorris and Gray considered the signicance of the induction forces even for the low energy cellulosic surfaces that they studied [31]. This aspect, however, has been overlooked in many subsequent investigations where k d derived from IGC experiments S have been reported for both low- and high-energy materials. It may be valid to assume that the interaction of gaseous alkanes with low energy surfaces, absent of appreciable electric elds, are dominated by dispersive (London) interactions. It should be noted that for the alkane/solid system, the Keesom orientation term, k v, is zero because n-alkane probe gases S do not possess a permanent dipole.

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3. Results

3.1. Sequential isothermal IGC analysis

The relationship between V o and the exposure S time, t, for the PCC sample with Tc =100C is shown in Fig. 3. In this logarithmic plot, V o S continually increases with the progression of the experiment for each of the alkanes tested. The change in V o is a direct indication of Ks because S the change in specic surface area is minimal, cf. Table 1. This indicates that the probe has an increased afnity for the PCC surface with the duration of the experiments. In all of the curves, the rate of change appears to occur in two phases. In the rst phase a linear change occurs until :3040 h when the rate of change diminishes. This may indicate either a change in the mechanism of adsorption of the gases or a change in the surface characteristics of the adsorbent. The effect of column temperature, Tc, was examined for PCC with hexane and octane at 60,

100, and 140C as shown in Fig. 4. Although V o S is observed to increase with exposure time at the three Tc values, there does not appear to be a signicant change in the trend with temperature. At the lower temperatures of 60 and 100C the k LW values for the different CaCO3 did not vary S signicantly with time. The PCC was tested at 140C where its initial value of k LW was 50 mJ m 2 and increased to 65 S mJ m 2 after 100 h. This evidently resulted from the effects of conditioning temperature on k LW S which will be examined in detail in the next section. The increase of V o with exposure time was also S determined with the marble and chalk I samples at 100C. Selected results are illustrated in Fig. 5 where V o values of heptane are plotted as a S function of t for each of the CaCO3 samples. The variation in V o is substantially different for the S three samples. The greatest relative increase in V o S was found for marble followed by PCC, and then chalk I, which changed very little. The range of C7

Fig. 3. Sequential isothermal analysis of precipitated calcium carbonate (PCC). Temperature of column during test (TC) was 100C. Specic retention volume of various alkanes is plotted as a function of exposure time.

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Fig. 4. Sequential isothermal analysis of precipitated calcium carbonate (PCC). Temperature of column during test (TC) was held at either 60, 100, or 140C. Specic retention volume of hexane and octane is plotted as a function of exposure time.

retention times, tp, cf. Eq. (1), that correspond to the curves illustrated in Fig. 5 are: PCC 0.97 2.1 min, marble 0.661.44 min, and chalk I 3.68 6.36 min. These values are subject to an experimental error of B1%. The behavior observed in these experiments indicates that the CaCO3 surfaces continually undergo physical and/or chemical changes even beyond 100 h. In view of these results, the CaCO3 samples were then examined following heating pretreatment.

3.2. Preconditioned IGC analysis

Fig. 6 shows the results from the analysis of the various CaCO3 samples and are expressed as k LW S (determined at 100C) versus preconditioning temperature, Tp. The marble and the PCC exhibit similar behavior k LW increases dramatically with S Tp \ 150C. The results calculated from the data of Ahsan et al. [19,30], Schmitt et al. [3] and Lundqvist et al. [21] are also included. There is close agreement between the results of these studies and this investigation for calcium carbonate

samples. There is also agreement between the results obtained for the marble sample, 57 mJ m 2, and those reported by Janczuk et al. [6] using contact angle on marble plates 64mJ m 2. The inuence of Tp on the observed k LW are also S apparent on the three other samples and the selection of a single preconditioning temperature to characterize the CaCO3 appears inappropriate. Chalk samples I and II both have high k LW values S and only small variation with Tp as compared to PCC and marble. It appears that the surfaces of the chalk samples require minimal conditioning to attain higher energies as compared to the PCC and marble (that require higher Tp to attain high energy surfaces). Fig. 7 shows the H o values for chalk I and A II, PCC, and marble samples that were conditioned at 200C. As with k LW, the chalk samples S had the highest energy of interaction and PCC had the lowest. The slope of H o versus A carbon number was also greater for the chalk I sample than the PCC and marble samples. This

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originates in higher values of G CH2 and thus A higher k LW values. S Fig. 8 shows the effect of the conditioning temperature on enthalpy of adsorption, H o , A for the PCC. A 25% increase in H o was A observed between heating at 200 and 300C. Direct determination of H o for temperatures B A 200C were not made because of the variation of V with time. In order to approximate H o of S A the samples before surface changes occur, a new parameter was introduced which is termed the intrinsic enthalpy of adsorption, [H o ]o. DeterA mination of [H o ]o involved the extrapolation of A V o values, cf. Fig. 4, to t = 1 min for each of the S temperatures tested. Three temperatures, 60, 100, and 140C, were included in the extrapolation for the PCC sample shown in Fig. 8. The [H o ]o A falls well below the preconditioned samples and also the standard heat of condensation, H o . C This could result from the mode of condensation of the alkane on surface sites as discussed theoretically by Kiselev [39].

4. Discussion

4.1. Pore structure

The variation in adsorption characteristics that occurs in the sequential isothermal IGC analysis may at rst appear to result from capillary condensation of the alkane probes in newly formed pores [40]. Carrott and Sing [41] in their work with porous carbons demonstrated that the adsorption energy, i.e. H o and k LW, signiA S cantly increased for samples with greater pore volume. The chalk I and chalk II sample gave relatively high, H o and k LW as compared to A S the PCC and marble samples which was at rst speculated to result from molecular sieving [25] in the internal porous structure. However, the BET surface area analysis, cf. Table 1, indicated that the chalk I sample had the lowest Asp which did not support the conjecture. In order to clearly resolve the inuence of the pore structure, a more detailed analysis was conducted to quantify the

Fig. 5. Sequential isothermal analysis of calcium carbonates. Specic retention volume of chalk I (mined), precipitated calcium carbonate (PCC), and ground marble are is plotted as a function of exposure time.

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Fig. 6. The apolar component of surface free energy for various calcium carbonates plotted as a function of the preconditioning temperature. The temperature of column was held at 100C during the test. The results from other investigators are also shown on the plot.

size distributions of the pores using nitrogen adsorption and mercury intrusion porosimetry. Fig. 9 illustrates the results of nitrogen adsorption porosimetry for the chalk I and PCC samples following a standard pretreatment at 200C for 24 h. Clearly the chalk I sample has less ne pore volume than the PCC sample. It may be inferred that the relatively high surface energetics observed with the chalk I sample is not the result of increased condensation of the alkanes in the pore structure. Earlier investigations [15,16] suggested that an increase in pore volume is associated with the removal of adsorbed water CaCO3. This aspect was explored in detail by analyzing the pore volume distributions of the PCC and chalk I samples before and after sample conditioning at 200C. The results are shown in Fig. 9 as a plot of DV/DD at various diameter intervals. For both CaCO3 samples, the pore volume increases with , heating at 200C for diameters less than 100 A. Table 3 provides the cumulative increase in pore

volume that occurs for PCC sample and chalk I , for DB 100 A following preconditioning at 200C. The chalk I sample, while having less overall pore volume, had a greater relative increase in the pore volume following heating. Whereas, it has already been demonstrated that the chalk I sample changed the least during sequential isothermal IGC analysis, cf. Fig. 5. This forties the conclusion that changes in the pore structure that occur during dewatering are not signicantly responsible for the differences in surface energetics that are observed in the IGC analyses.

4.2. The role of water

The evolution of water from the samples by desorption of the physisorbed water or by dehydroxylation of Ca(OH)2 was expected to occur in all of the CaCO3 samples under the conditions of the sequential isothermal IGC analysis and in preconditioning [17]. To quantify the effects of

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adsorbed water on V, columns that had been S previously heated to 100 C for more than 100 h were purged with saturated water vapor for 24 h, and again subjected to sequential isothermal IGC analysis. The results for PCC with hexane, octane and decane are shown in Fig. 10. The very close agreement between the two curves suggests that the changes in adsorption are directly related to the presence or absence of water at the surface. A similar experiment was conducted using CO2 instead of water vapor to purge the column. The V o values were unaffected by CO2 treatment indiS cating insignicant change in the surface energetics. Several investigators [8,9,17] have demonstrated that the CaCO3 decomposes very slowly at temperatures below 300C. The resulting CaO may provide sites that give different V o S values and are readily hydroxylated to chemisorb water. The effects of chemisorbed water on the surface energetics of mineral oxides were investigated by Suda et al. [38,42]. They found that the electrostatic eld strength of the materials was inversely proportional to the surface hydroxyl concentration. Fig. 11 shows a plot of k LW versus the S

Fig. 8. Differential enthalpy of adsorption of precipitated calcium carbonate after preconditioning at 100, 200, or 300C. The plot shows the heats of condensation of the alkanes (DHC) Also shown are the DHa indicating the initial state values determined by extrapolation of sequential isothermal plots.

estimated monolayer coverage of water for the three CaCO3 samples. Monolayer water coverage was calculated using the total weight loss during conditioning and a molecular area of water of , 10.4 A2 [29]. The estimation assumes that the weight loss is entirely as a result of water from the surface and that the water is completely desorbed

Fig. 7. Differential enthalpy of adsorption of alkanes on the CaCO3 surfaces. All samples were preconditioned at 200C for 24 h.

Fig. 9. Pore size distribution of precipitated calcium carbonate (PCC) and chalk with and without preconditioning at 200C.

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Table 3 Pore volume characteristics of PCC and chalk I Sample Pore volume B D Pore volume , 100 A (103cc1 g1) (103cc1 g1) (mg1 m2)

PCC Not conditioned Conditioned 4.17 at 200C Chalk I Not conditioned Conditioned 1.71 at 200C

3.47 0.70 0.88

1.23 0.48 1.38

at 300C. The difference between the different forms of CaCO3 is apparent. The results from Chassin et al. [43] in their investigation of Ca-montmorillonite using contact angle measurements are also included in Fig. 11. Note the similarity in the

curves as k LW decreases with the adsorbed water S concentration. Dorris and Gray observed a similar trend with water on silica [44]. The effect of water on decreasing the interactions of gaseous alkanes with CaCO3 surfaces has been reported by several investigators [7,14]. The water acts to present a low energy surface to the non-polar molecules vapors [45,46] and interacts mostly because of dispersion (London) forces. In IGC, this is manifested as shorter observed retention times. When dry heating desorbs the water layer, highly polar sites are exposed which increases the magnitude of the dispersion (London) and induction (Debye) forces substantially [38]. Fig. 12 illustrates a model of the surface that accounts for the change in k LW that accompanies the desorption of water S from the CaCO3 surface. Trace amounts of contaminants at the surface, e.g. silica or iron, may contribute to the increased surface energies of the chalk samples. Although important differences in the surface energetics of the three CaCO3 samples exist, identication of the origin of such differences is still under investigation.

Fig. 10. A comparison of the sequential isothermal analysis of precipitated calcium carbonate before (solid symbols) and after (open symbols) regeneration with water vapor. The temperature of column was held at 100C during the test.

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Fig. 11. The apolar component of the surface free energy plotted as a function of the apparent monolayer water coverage of CaCO3 samples.

5. Conclusions The usefulness of IGC for identifying differences in the surface chemistry of calcium carbonates was demonstrated in this investigation. The method appears quite sensitive to the changes in surface energetics that result from desorption of surface water at submonolayer concentrations. Non-polar probe gases were used to monitor the change in the apolar component of surface free energy as samples were subjected to preconditioning at temperatures between 100 and 300C, referred to as preconditioned analysis. PCC exhibited a substantial increase from : 50 mJ m 2m to : 250 mJ m 2. Ground marble showed similar behavior to the PCC. Two chalk samples had much greater apolar components (: 140 and 180 mJ m 2) and showed less change with preconditioning temperature. Sequential isothermal analysis was introduced as a method for monitoring the change in the test

sample imparted by the carrier gas sweep of the IGC test. Dehydration that occurs during the test changes the energetics of interaction of the probe adsorbates well beyond the conventional conditioning time of 24 h. The dynamic state of the test column can interfere with the measurment of enthalpy of adsorption, and apolar component of surface energy if such changes are not considered. Continuation of this investigation has included IGC experiments under equilibrium conditions where the water in the carrier gas is held constant at very low concentrations.

Acknowledgements The authors would like to thank N. Sanders of Specialty Minerals Inc. for providing PCC samples, and P.R. Suitch and R.J. Pruett of ECC International for conducting sample analyses. The efforts of D. Driscoll, R. Hanna, and A. Day of

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D. Ste6en Keller, P. Luner / Colloids and Surfaces A: Physicochem. Eng. Aspects 161 (2000) 401415 [2] P. Schmitt, E. Koerper, J. Schultz, E. Papirer, Chromatographia 25 (1988) 786. [3] E. Papirer, J. Schultz, C. Turchi, Eur. Polym. J. 20 (1984) 115. [4] T. Ahsan, B.A. Colenutt, K.S.W. Sing, J. Chromatogr. 479 (1989) 17. [5] T. Okayama, D.S. Keller, P. Luner, J. Adhes. 63 (1997) 231. [6] B. Janczuk, E. Chibowski, P. Staszczuk, J. Colloid Interface Sci. 96 (1983) 1. [7] S.J. Gregg, R. Stock, in: D.H. Desty (Ed.), Gas Chromatography, Academic Press, New York, 1958. [8] G. Goujon, B. Mutaftschiev, J. Colloid Interface Sci. 57 (1976) 148. [9] W.H. Wade, N. Hackerman, J. Phys. Chem. 63 (1959) 1639. [10] D. Morel, F. Stoeckli, F. Krahenbuhl, L. Misteli, P. Munyazikwiye, Helvetica Chimica Acta 68 (1985) 1844. [11] W. Neagle, C.H. Rochester, J. Chem. Soc. Faraday Trans. 86 (1990) 181. [12] N. Sanders, Proceedings of the 1991 Symposium on Papercoating Fundamentals, Tappi Press, 1990. [13] N. Hackerman, A.C. Hall, J. Phys. Chem. 62 (1958) 1212. [14] R.B. Gammage, S.J. Gregg, J. Colloid Interface Sci. 38 (1972) 118. [15] R.B. Gammage, H.F. Holmes, E.L. Fuller Jr, D.R. Glasson, J. Colloid Interface Sci. 47 (1974) 350. [16] T. Ahsan, K.S.W. Sing, Colloids and Surfaces 64 (1992) 167. [17] T. Morimoto, J. Kishi, O. Okada, T. Kadota, Bull. Chem. Soc. Jpn. 53 (1980) 1918. [18] D.R. Lloyd, T.C. Ward, H.P. Schreiber and C.C. Pizana, Eds., Inverse Gas Chromatography, Am. Chem. Soc. Symposium No. 391 pp. 168 184, 1988. [19] T. Ahsan, D.A. Taylor, J. Adhesion 67 (1998) 69. , 8 [20] A Lundqvist, L Odberg, J.C. Berg, Tappi J. 78 (1995) 139. , 8 [21] A. Lundqvist, L. Odberg, in: Proc. Int. Paper and Coating Chemistry Symp., June 11 13, 1996, Ottawa, Ontario, (CPPA, Montreal, 1996) pp. 29 34 [22] H.-L. Lee, P. Luner, Nordic Pulp Paper Res. 4 (1989) 164. [23] M. Pyda, M. Sidqi, D.S. Keller, P. Luner, Tappi J. 76 (1993) 79. [24] S. Dong, M. Brendle, J.B. Donnet, Chromatographia 28 (1989) 469. [25] J.R. Condor, C.L. Young, Physiochemical Measurement by Gas Chromatography, Wiley, New York, 1979. [26] M. Ciganek, M. Dressler, Polymer Composites 10 (1989) 194. [27] E. Hakanen, J. Koskikallio, Finn. Chem. Lett. 1982, 34. [28] E.P. Barret, L.G. Joyner, P.H. Halenda, J. Amer. Chem. Soc. 73 (1951) 373. [29] S.J. Gregg, K.W.S. Sing, Adsorption, Surface Area and Porosity, 2nd Ed., Academic Press, New York, 1982. [30] T. Ahsan, B.A. Colenutt, K.S.W. Sing, J. Chromatogr. 464 (1989) 416. [31] G.M. Dorris, D.G. Gray, J. Colloid Interface Sci. 77 (1980) 353.

Fig. 12. Proposed mechanism for the increase in the apolar component of surface free energy with thermal pretreatment and dry sweep dehydration. With mild preconditioning, bound water is retained at the calcium carbonate surface and tends to shield the electric eld. The induced (Debye) component is negligible. As the heat and dry gas sweep of rigorous preconditioning remove water, the electric eld of the crystal surface is exposed inducing a dipole in the dilute alkane molecules. The induced (Debye) component is by the increased interaction between the permanent dipole of the CaCO3 crystal and the induced dipoles in the alkane molecules.

State University of New York, College of Environmental Science and Forestry, Ultrastructure Studies Laboratory, for performing ICP/AES analyses and SEM microphotography are also appreciated. The authors would also like to thank M. Sidqi of Sandoz for helpful discussion and insight. The nancial support of the Empire State Paper Research Associates (E.S.P.R.A.) is gratefully acknowledged.

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