Kinetics of crystal growth of calcium sulfate dihydrate.

The influence of polymer composition, molecular weight, and solution pH

ZAHID AMJAD
The BFGoodrich Cornparzy, Avon Lake, Techrzical Center, Avorz Lake, OH 44012, U.S.A.

Received October 23, 1987

ZAHID AMJAD. Can. J . Chem. 66, 1529 (1988). A seeded crystal growth technique has been used to study the influence of solution pH and temperature ranging from 25 to 50C on the performance of polymers of varying functional groups as calcium sulfate dihydrate (CaS04.2H20,gypsum) crystal growth inhibitors. Results indicate that at constant temperature and at a constant solution pH, crystallization in the presence of polyacrylic acids is preceded by an initial slow growth reaction, hcreaftcr called induction period, following which crystal growth of gypsum proceeds with a rate close to that in pure supersaturated solution. Results suggest that at a constant pH, polyacrylic acid concentration, molecular weight, and temperature greatly affect the duration of induction period. Kinetic data collected as a function of solution pH in the range 2.5 to 9.0 suggest that solution pH has a marked effect on the induction period. The observed dependence of induction period on solution pH may be explained in terms of the degree of ionization of polyacrylic acid. Among the polymers of varying functional groups studied, i.e. carboxyl, sulfonate, acrylamide, dimethyldiallylammonium, etc., only those polymers having carboxyl group showed marked inhibitory activity for the growth of gypsum crystals. ZAHID AMJAD. Can. J . Chem. 66, 1529 (1988) On a fait appel i une technique de croissance de cristaux ensemencCs pour Ctudier I'influence du pH de la solution ainsi que de la tempkrature (allant de 25 i 50C) sur la performance de polymkres portant divers groupements fonctionnels comme inhibiteurs de la croissance de cristaux du sulfate de calcium dihydratC (&SO4. 2H20, gypse). Les rCsultats indiquent que, i tempCrature constante et i un pH de solution constant, la cristallisation en prCsence d'acides polyacryliques est prCcCdCe par une rCaction initiale de croissance qui est lente, appelCe par la suite pCriode d'induction, et qui est suivie par une croissanee du cristal de gypse se produisant i une vitesse qui est proche de celle qui est observie avec une solution sursaturke pure. Les rCsultats suggerent que, i des pH constants, la concentration en acide polyacrylique, le poids molCculaire et la tempirature influencent beaucoup la pCriode d'induction. Les donnCes cinCtiques recueillies en fonction du pH allant de 2,5 2 9,O suggtrent que le pH de la solution a une influence marquCe sur la pCriode d'induction. On peut expliquer cette observation en fonction du degri d'ionisation de I'acide polyacrylique. Parmi les polymeres portant divers groupements fonctionnels, eomme carboxyle, sulfonate, acrylamide, dirnithyldiallylammonium, etc, seuls les polymeres portant des groupements carbonyles prisentent une activitC inhibitrice marquee sur la croissance des cristaux de gypse. [Traduit par la revue]

Introduction
Considerable attention has been given to the various forms of calcium sulfate crystallizing from aqueous solution as affected by temprature, p H , solution stoichiometric ratio of lattice ions, and impurities level (1-4). These and other important factors involved in the nucleation and growth of calcium sulfate dihydrate (CaS04. 2 H 2 0 , gypsum), hemihydrate ( C a S 0 4 . $ H 2 0 , plaster of Paris), and anhydrite ( C a S 0 4 ) should have direct application to the control and inhibition of scale formation in industrial water systems, oil production, geothermal, and desalination systems (5-7). In many cases the deposition of hard crystalline scale on heat transfer surfaces results in decreased thermal efficiency of the system. T o preclude an excessive rise of operating costs, scale formation has to be prevented. The effectiveness of a number of inhibitors in preventing o r reducing the crystallization of calcium sulfate has been the subject of numerous investigations. McCartney and Alexander (8) have examined the effect of a number of polyelectrolytes on the growth rate of calcium sulfate dihydrate. It was found that polymers-containing carboxyl groups such as carboxymethyl cellulose, aliginic acid, polymethacrylic acid, and polyacrylic acid were particularly effective as C a S 0 4 . 2 H 2 0 crystal growth inhibitors. Kuntz (9) arrived at similar conclusions after studying the effect of various protein hydrolyzates and their synthetic analogues o n the crystallization of calcium sulfate. The influence of molecular weight on the polyelectrolytes on the precipitation of C a S 0 4 . 2 H 2 0 from aqueous solutions have

been the subject of numerous investigations. Jones (10) in his study on the effect of molecular weight (50 000 - 400 000) of carboxymethyl cellulose (CMC) reported that high molecular weight C M C polymers were the least effective and the effectiveness increases as the molecular weight of the polymer decreases. Flesher et al. (1 1) in their study on the evaluation of a variety of polyelectrolytes at high temperature, as C a S 0 4 . 2 H 2 0 scale inhibitors showed that the efficiency of the polyelectrolyte decreases with increasing molecular weight in the range 2 000 750 000. Amjad (12) in a recent study on the influence of polyacrylates in controlling C a S 0 4 . 2 H 2 0 dihydrate scale formation on heat transfer surfaces reported that the molecular weight of the polyacrylate plays an important role in the inhibition of C a S 0 4 . 2 H 2 0 crystal growth from aqueous solution. The amount of C a S 0 4 . 2 H 2 0 scale deposited on heat exchanger was found to be higher in the case of higher molecular weight polyacrylate (mw = 240 000) than that obtained in the presence of 2 100 molecular weight polyacrylate. Several studies have been reported on the influence of solution pH on the performance of polymeric and non-polymeric inhibitors on the crystal growth of sparingly soluble salts. Recently Griffiths et al. (1 3) have shown that the performance of phosphonic acids as C a S 0 4 . 2 H 2 0 crystal growth inhibitor improves with increasing pH, and have attributed this improvement to an increase in the degree of deprotonation. Leung and Nancollas (14), using seeded growth technique, arrived at similar conclusions after studying the effect of benzene polycarboxylic acids o n the crystal growth of B a S 0 4 . Recently,

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TABLE 1. Analytical characteristics of polymers Polymer Composition Poly(acry1ic acid) (K-XP75) Poly(acrylic acid) (K-XP74) Poly(acrylic acid) Poly(acry1ic acid) Poly(acry1ic acid) Poly(acry1ic acid) Poly(acry1amide) Poly(dimethy1diallylammonium chloride) Poly (isopropy lacrylamide) Poly(2-acrylamido-2-methyl propane sulfonic acid) Acronym P-AA P-AA P-AA P-AA P-AA P-AA P-Am P-DMDAAC P-iPrAm P-SA Mol. wt. 2 600 6 000 10 000 22 000 50 000 800 6 000 6 000 10 000 10 000

Sheehan and Nancollas (15) have examined the effect of pH in the range 6-9 on the growth rate of C a C 2 0 4 . H 2 0 in the presence of polyacrylate. It was found that the rate of growth was independent of solution pH over the p H range studied. Because of the recent interest in the inhibitory effect of polymeric carboxylic acids as crystal growth inhibitors for sparingly soluble salts, in the present work the seeded growth method has been used t o investigate the influence of solution pH in the range 2.5-9.0, o n the rate of CaSO,. 2 H 2 0 crystal growth in the presence of poly(acry1ic acid) (mw 2 600 - 5 0 OOO), poly (acrylamide), poly (isopropylacrylamide), poly (2-acrylamido Zmethylpropane sulfonic acid), and poly(dimethy1diallylammonium chloride).

M. Solution pH CaS04 solution concentration would be 3.50 x was controlled by the addition of buffers at a total conjugate acid/base concentration of 2.0 x M, a concentration at which the influence of the buffering components on the rate of crystal growth was proved to be negligible. Polymers were added after the addition of CaCI2, but before the addition of Na2S04, as dilute solutions in water. Crystal growth was initiated in these supersaturated solutions by the addition of a known weight of seed crystals and the reaction monitored by analyzing aliquots of the filtered (0.22 micron filter, Millipore) solution for calcium by EDTA titration.

Results and discussion

The analytical characteristics of the polymers and the experimental conditions used in this study are summarized in Tables 1 and 2 , respectively. T h e typical curves for calcium concentrations against time are shown in Fig. 1. It can b e seen that the growth of C a S 0 4 . 2 H 2 0 takes place immediately upon the addition of gypsum seed crystals to the metastable supersaturated solutions. T h e rate of crystal growth, R , of C a S 0 4 . 2 H 2 0 from supersaturated solutions containing equivalent concentration of ions has been found to follow an equation of the forni

Experimental
Reagent grade chemicals and grade A glassware were used. Stock solutions of calcium chloride and sodium sulfate were prepared using distilled water, filtered through 0.22-km filter paper (Millipore Corp.) and analyzed as described previously (4). The polymers used in this study were selected from the range of commercial and experimental (BFGoodrich Chemical) materials. Polymer concentrations given in this report are on dry polymer basis. All polymers were tested under equal growth conditions, i.e. at the same supersaturation and pH of the bulk solution. Some of the polymers were also tested at different pH values. Buffers employed for pH control were acetic acid/sodium acetate, trihydroxymethylaminomethane/ trishydroxy methylaminomethane hydrochloride, and ammonia/ammonium chloride. pH was measured at 25C using a Brinkmann pH meter (model 632, Brinkmann Instruments, Westbury, NY) equipped with a pair of glass and calomel electrodes. The system was calibrated before each set of measurements and checked afterwards, against NBS standard buffers. Calcium ion analyses were performed by standard EDTA titration. Calcium sulfate dihydrate crystals were prepared (4) by the slow dropwise addition of 500 mL of 0.2 M calcium chloride solution to 500 mL 0.2 M sodium sulfate solution at 70C. The crystals were washed repeatedly with distilled water until free of chloride ions and were aged at least six months before being filtered to get dry powder for use in the crystal growth experiments. The crystals were characterized by X-ray powder diffraction. As described elsewhere (1, 4, 16) the seeded crystal growth of a sparingly soluble salt provides a sensitive and reproducible technique for the evaluation of inhibitor effects. The technique involves the addition of a fixed amount of seed crystals to a metastable solution of the inorganic salt followed by periodic analysis for changes in the salt concentration. In the present study, seeded crystal growth experiments were conducted in a stirred double-walled glass cell maintained at 25"C, containing a metastable calcium sulfate solution. The metastable solution (150 mL) was prepared by carefully mixing equimolar volumes of calcium chloride and sodium sulfate such that the final

in which TCa is total calcium concentration at time t , T,Ca is the equilibrium solubility value, k is a rate constant, s is a function of number of available growth sites present in the seed crystals, and t is the time in minutes. Figure 2 illustrates the linearity of the plots of the integrated form of eq. [ I ] . Reproducibility is illustrated by the agreement between the results of experiments 2 and 5 , respectively. Results of exoeriments 3 and 5 in Table 2 indicate that the rate of crystallization is directly proportional to the amount of seed crystals added initially. This confirms that crystallization occurred only on the added seed material, without any secondary nucleation or spontaneous precipitation. Studies were made on the rate of C a S 0 4 . 2 H 2 0 seed crystal growth at 25OC and p H values from 2 . 5 t o 9.0 in buffered calcium sulfate supersaturated solutions. Typical plots of the data plotted according to the integrated form of eq. [ I ] are shown in Fig. 3. Rate data summarized in Table 2 show that in the pH range 3.5-9.0, second-order rate constant is independent of solution pH, indicating that the bisulfate ion, which was suggested to be rate controlling in the crystallization of the hemihydrate at higher temperatures ( 7 ) , had a negligible influence on the seeded crystal growth of calcium sulfate dihydrate. Results presented in Table 2 for seeded growth experiments conducted in buffered solution show that rate

AMJAD

TABLE 2. Kinetic data for calcium sulfate dihydrate crystal growth in the presence of polymers
TCaS04 = 3.50 X lo-' M Dosage Seed T ( P P ~ ) (mg) ("0 pH

Expt. 2 3 5 8 10 4 12 13 16 14 20 18 23 26 21 30 28 25 32 33 29 31 36 34 37 39 40 38 27 35 24 41 42 44 46 48 49 52 51 56 54 57 59 62 61 60 64 66 65

Polymer None None None None P-AA (cornrn. B) P-AA (cornrn. B) P-AA (cornrn. B) None P-AA (cornrn. B) None P-AA(c0rnrn.B) None P-AA (cornrn. B) None P-AA (cornrn. B) None P-AA (cornrn. A) P-AA (cornrn. B) P-AA (cornrn. B) P-AA (cornrn. B) P-AA (cornrn. B) P-AA (exp. C) P-AA (exp. D) P-AA (exp. D) P-AA (exp. E) P-AA (exp. E) P-AA (exp. F) P-DMDAAC (exp. G) P-Am (exp. H) P-iPrArn (exp. J) P-SA (exp. I) None P-AA (cornrn. B) None P-AA (cornrn. B) None P-AA (cornrn. A) P-AA (cornrn. B) P-AA (exp. C) P-AA (exp. D) P-AA(exp.E) P-AA (exp. F) None P-AA (cornrn. A) P-AA (cornrn. B) P-AA (exp. C) P-AA (exp. D) P-AA (exp. E) P-AA (exp. F)

Induction time (rnin)

10 ks (M-' r n i n ' )

"Unbuffered solution.

constants are within &6% of that in the unbuffered solution. This suggests that buffering components at a total conjugate acid/base concentration of 2.0 x l o p 3 M does not have any significant effect on the rate of crystal growth. Table 2 summarizes the results of crystal growth experiments made in the presence of polymers. Figure 4 illustrates typical growth curves at pH 7.0 in the presence of commercial polymer B (mw 6 000). As shownin Fig. 5, thecrystallization reaction in the presence of 0.25 ppm of commercial polymer B is preceded by an induction period of 240 min after which the rate

commences with a measurable rate. Figure 4 further indicates that an increase in polymer concentration only results in a prolongation of the induction period and at a 1.0 ppm polymer concentration, the rate of crystallization was completely inhibited for at least 20 h. Table 2 also shows data on induction periods as a function of polymer concentration for commercial polymer B. It can be seen (exps. 25, 32, 33, 39, Table 2) that the duration of the induction period is greatly increased by increasing the polymer concentrations. Representative plots of the integrated form of eq. [l] in the

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TI ME (mrn)
Plots of total calcium (TCa) against time. The effect of seed concentration: (0) 200 mg, ( A ) 197 mg, ( 0 ) 320 mg, 25C.

FIG.2. Kinetic plots of eq. [1] for the CaSOs.2H20 crystal growth: ( 0 ) 200 mg, ( A ) 197 mg, (0) 320mg. 25C.

presence of varying concentration of commercial polymer B shown in Fig. 5 demonstrate the success of this rate equation in interpreting the results in the presence polymer. As shown in Table 2 the rate of crystal growth of CaS0,. 2H20 following the induction period has very little correlation with the concentration of polymer. A similar temporarily growth inhibition was reported in the seeded growth of CaS04. 2H20 in the presence of phosphonates, polyphosphonates, and other polyelectrolytes (17, 18). It is also interesting to note that seeded growth of

BaS04 in the presence of trace amount of sodium tripolyphosphate, Liu and Nancollas (19) found that crystallization reaction following the initial induction period takes place at a rate comparable to the rate of crystallization from pure solution. The influence of pH on the performance of several phosphonic acids as CaS04.2 H 2 0 crystal growth inhibitors has been recently studied by seeded growth technique (13). Results of this study show that an increase in the pH of the crystal growth medium over a pH 4 to 9 range brings about an improvement in

AMJAD

FIG.3. Kinetic plots of eq. [I] for the C a S 0 4 . 2 H z 0 crystal growth as a function of solution pH. pH 8.5 (unbuffered), 25C. (unbuffered), ( V ) pH 6.5 (buffered), (0)

(O), ( A ) pH 7.0 (buffered), (a), pH 5.5

FIG.4. Plots of TCa as a function of time in the presence of comm-B polyacrylate at pH 7.0,25"C. The effect of polymer concentration (ppm): ( A ) 0.0, (0) 0.10, (0) 0.25, ( V ) 0.35, (0)1.0, (0.35 ppm and 1.0 ppm lower time scale).

inhibitor performance that runs parallel to the phosphonic acid titration curve. For polymeric inhibitors, such as polyacrylic acids, the degree of deprotonation should, just as phosphonate inhibitors, be considered in explaining their action. Unfortunately their acid dissociation constants are not available. It can nevertheless be expected that the affinity of polymeric inhibitor molecules towards the crystal surface should also be influenced by the solution pH due to the dissociation of the carboxylic acid group.

The effect of the solution pH on the crystal growth of CaS04.2H20 in the presence of commercial polymer B was studied using the seeded growth technique. The results presented in Table 2 indicate that at constant temperature and polymer concentration (0.25 ppm), the induction time is strongly dependent upon solution pH. For example, the induction times observed at pH 2.5, 3.5, 5.5, 7.0, and 9.0 are 0 , 170, 230, 240, and 260, respectively. Data in Table 2 demonstrates the ineffectiveness (induction time < 2 min), of commercial poly-

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3G0

TIME(rnln)

GOO

FIG.5. Kinetic plots of eq. [ l ] for the growth of CaS04.2H20in the presence of varying concentration of comm-B polyacrylate at pH 7.0, 0.25, ( V ) 0.35, (0)1.0 (0.35 ppm and l.0ppm lower time scale). 25C. (U)0.0, ( A ) 0.10, (0)

mer B as an CaS04.2H20 crystal growth inhibitor at pH 2.5 and at 0.25 to 1.0 ppm of polymer concentration. It should be noted that under similar conditions at pH 7.0 induction times observed for commercial polymer B at 0.25 and 1.0 ppm were 240 and > 1200 min respectively. The poor inhibitory performance exhibited by commercial polymer B at pH 2.5 may be explained due to insignificant deprotonation of carboxylic acid group at this pH value. Although it has been reported (20) that adsorption capacity of polyelectrolyte increases with decreasing pH values, the absence of induction time or relatively poor performance of commercial polymer B at pH 2.5 may be explained due to insufficient electrostatic interaction of inhibitor molecule at the crystal surface, since at pH 2.5 inhibitor molecule will have very low anionic charge density. Thus at low pH values polymeric inhibitor i.e. commercial polymer B acts like non-ionic polymer and perhaps acquires a loopy configuration at the crystal surface. As shown in Table 2 the induction times observed for commercial polymer B at 0.25 ppm concentration are 0, 170, and 230, at pH 2.5, 3.5, and 5.5, respectively. However, upon raising the solution pH from 5.5 to 7 to 9, no significant increase in induction times were observed. This suggests that the deprotonation of commercial polymer-B may near complete at pH = 6 or higher. The influence of polymer structure as CaSO4.2H20 crystal growth inhibitor at 0.25 ppm concentration and at pH 7.0 was also studied at the same calcium sulfate supersaturation. Kinetic data for polymers of varying functional group, i.e. acrylamide, isopropylacrylamide, 2-acrylamido-2-methylsulfonic acid, and quartemaryamine, etc., are summarized in Table 2. The results on these polymers (exps. 38, 27, 24, 35) which do not contain carboxyl group show that at 0.25 ppm of polymer concentration these polymers do not show any significant effect on both the induction period and the rate of crystal growth. The effect of the molecular weight of polyacrylates at a concentration of 0.25 ppm was studied using the seeded growth technique. The results are presented in Table 2. Typical growth

curves in the presence of polyacrylates of varying molecular weight are shown in Fig. 6. Data shown in Table 2 indicates that at pH 7.0, 25"C, and constant polymer concentration, the induction time increases with decreasing molecular weight from 20 000 to 2 600 and thereafter decreases with decreasing molecular weight (2 600 - 800). In addition, the rates of crystal growth in the presence of polyacrylates of varying molecular weight (Table 2) are within 2 7 % of the rate in pure solution. Figure 7 illustrates the effect of molecular weight of polyacrylates on the induction period at various temperatures. It can be seen that an increase in temperature only results in reduction of induction period. Recently, the influence of a variety of polyelectrolytes in controlling scale formation has attracted the attention of several investigators. It is generally agreed that the polyelectrolytes which have an effect on controlling scale formation are highly substituted with carboxyl groups. In addition, it has also been shown that one of the factors determining the effectiveness of a polyelectrolyte is its molecular weight. Williams and Ruehrwein (21) suggested that molecular weight influences the kinetics of adsorption of the polyelectrolyte onto the growing crystals. It was postulated that there should be an optimum molecular weight for a given polyelectrolyte at which maximum effect would be obtained. In the discussion on the effect of a variety of polyelectrolytes on crystal growth of CaS0,. 2H20, Smith and Alexander (22) suggested that the adsorbed polymer molecules acted as immobile impurities on the crystal surface and that they inhibited crystal growth by reducing the rate of step movement across the crystal surface. In addition, growth inhibition was found to be strongly dependent on the structure and the molecular weight of the polyelectrolyte. Based upon the results for the similar molecular weight polyelectrolyte, Smith and Alexander (22) reported that polyacrylic acid was more effective than polymethacrylic acid. Furthermore, growth inhibition results for series of experiments with styrene maleic anhydride copolymers suggest an optimum effectiveness with molecular weight of 1600 for this polyelectrolyte. Recently

AMJAD

FIG. 6. Plots of TCa against time for CaS04.2H20 crystal growth in the presence of 0.25 ppm polyacrylate at pH 7.0, 25C. The effect of polymer molecular weight ( 0 ) control (no polymer), ( 0 ) 22 000, ( A ) 6 000, (0) 2 600, (2 600 mol. wt. - lower time scale).

12 POLYMER MOL. WT. xi000

20

FIG. 7. Relationships of induction periods with polyacrylate molecular weight for the crystal growth of CaS04.2H20at varying temperature ("C): ( A ) 25, ( 0 ) 35, ( 0 ) 50; polymer concentration = 0.25 ppm, pH 7.0.

Libutti et al. (23) in their study on the evaluation of polyacrylates as antiscalants for cooling water applications showed that the rate of fouling increases with an increase in molecular weight in the range 2 000 - 100 000. In summary, the results presented in this paper on the influence of polymers of varying functional groups as CaS04.2H20 crystal growth inhibitors, show that the most effective inhibitors are those which are highly anionic in nature (e.g., carboxyl group in polyacrylic acid) whereas cationic charged polymers do not exhibit any significant inhibitory activity. This observation is consistent with results of earlier investigations on the effect

of various anionic charged additives such as polyphosphate, phosphonate, polyaspartic acid, and phosphonocarboxylic acid, as crystal growth inhibitors for barium sulfate, calcium carbonate, and calcium oxalate. The results presented in this paper on CaS04.2H20 crystal growth inhibition by polyacrylic acid suggest an optimum effectiveness with molecular weight of -2 000. At values below 2 000 a marked decrease in the polyacrylic acid effectiveness occurs with decreasing molecular weight, which can be due to a decreasing number of bonding possibilities. The same tendency is observed with increasing values of the molecular

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CAN. J. CHEM. VOL. 66, 1988

weight above -2 000. This is rather surprising since the number of bonding possibilities increases with increasing chain lengths. It is not likely that large molecules adopt a "loopier" configuration with less effective bonds than smaller ones, since even very high molecular weight polyelectrolytes appear to be able to adopt a flat configuration upon the crystal surface, in spite of the entropy lost in a flat configuration (20). T h e phenomenon of a markedly decreasing polyacrylic acid effectiveness with increasing molecular weight above -2 0 0 0 can thus not be explained. Adsorption studies are currently underway in our labs to better understand the role of molecular weight of polyacrylic acid and acrylic acid-based copolymers of varying compositions and functional groups in inhibiting crystal growth of sparingly soluble salts in aqueous solutions. In the industrial application of these polymers a s scale inhibitors, the presence of induction period observed for crystal growth in the presence of polyacrylic acids, may be perfectly acceptable provided that the induction period is longer than the period required for scale protection. Mechanism of C a S 0 4 . 2 H z 0 crystal growth inhibition The marked effect of P-AA on the induction period preceding the crystal growth of gypsum from supersaturated solution may be attributed due to one or more of the following factors: (1) P-AA may change the ionic strength of the solution and hence the effective solubility of the calcium sulfate; ( 2 ) P-AA may form stable complexes with calcium ion and reduce supersaturation; (3) the inhibitor may be adsorbed on the crystal surface either generally o r at the active growth sites. Under the experimental conditions employed in the present investigation the presence of induction period preceding the crystal growth must be attributed to the surface adsorption factor rather than calcium-P-AA complex formation or the concomitant increase in ionic strength of the supersaturated solution in the presence of poly(acry1ic acid). The results discussed in this paper on C a S 0 4 . 2 H 2 0 crystal growth inhibition by a variety of inhibitors suggest that those inhibitors under this study can be classified into the following two general categories: ( a ) Those such a s poly(isopropylacrylamide), poly(acrylamide), and poly(2-acrylamido-2-methyl-2 propane sulfonic acid), and poly(dimethyldially1 ammonium chloride), which have no pronounced effect on the rate of C a S 0 4 . 2 H 2 0 crystal growth and show induction period of less than 2-5 min. (b) Those such as poly(acry1ic acid) which also exhibit no significant effect on the rate of C a S 0 4 . 2 H 2 0 crystal growth but show rather well-defined induction periods (few to several hundred minutes). In addition. the duration of the induction periods is greatly influenced by changing the concentration of poly acrylic acid. The striking effect of the polyacrylic acid on the induction periods with subsequent growth of C a S 0 4 . 2 H 2 0 observed in the present study may be explained by an incorporation of polyacrylic acid into the growing crystals. During the induction period,most of the active growing sites may be poisoned by adsorbed polyacrylic acid molecules. However, some of the

growth sites of lower energy may still be free to grow, and the reaction proceeds at a very slow rate. The changes in solution concentration during this stage may be too small to be detected. After these slowly advancing steps cover the poisoned sites, the adsorbed molecules are incorporated into growing crystal and the crystal growth can resume at a rate comparable to that of unpoisoned systems.

Acknowledgement
The author wishes to thank Dr. William F. Masler for polymer synthesis, Glenn Evans for experimental assistance, and The BFGoodrich Company, Specialty Polymers & Chemicals Division for support in publishing this work. 1. G. H. NANCOLLAS, M. M. REDDY, and F. TSAI. J. Crystal Growth, 20, 125 (1973). and J. ZAHAVI. Ind. Eng. Chem. Fundamentals, 9, 2. D. HASSON 1 (1970). 3. M. TADROS and I. MAYES. J. Colloid Interface Sci. 72, 245 (1979). 4. Z. AMJAD. Desalination, 54, 263 (1985). 5. P. H. RALSTON. J. Pet. Tech. 21, 1029 (1969). 6. P. F. ROLFE. Desalination, 1, 539 (1966). 7. A. E. AUSTIN, J . F. MILLER, N. A. RICHARD, and J. F. KIRCHER. Desalination, 16, 33 1 (1975). 8. E. R. MCCARTNEY and A. E. ALEXANDER. J . Colloid Sci. 13, 383 (1958). 9. R. A. KUNTZE. Nature (London), 211, 406 (1966). Corrosion, 17, 232 (1961). 10. L. W. JONES. 11. P. FLESHER, E. L. STREATFIELD, A. S. PEARCE, and 0. D. HYDES. 3rd Int. Symp. Freshwater Sea, 1, 493 (1970). 12. Z. AMJAD.4th Mexican Water Conference, Mexico City, Mexico. 1984. Paper 84- 19. 13. D. W. GRIFFITHS, S. D. ROBERTS, and S. T. Lru. Int. Symp. Oilfield Geothermal Chem. Society of Petroleum Engineers, 1979. Paper 7861. 14. W. H. LEUNG and G. H. NANCOLLAS. J. Inorg. Nucl. Chem. 40, 187 (1978). 15. M. S. SHEEHAN and G. H. NANCOLLAS. Investigative Urology, 17, 446 (1980). J. Crystal Growth, 6, 281 16. S. T. LIU and G. H. NANCOLLAS. (1970). 17. S. T. LIU and G. H. NANCOLLAS. J . Colloid Interface Sci. 52, 593 (1975). and F. SWEET. J. Colloid Interface Sci. 37, 612 18. B. R. SMITH (1971). 19. S. T. LIU and G. H. NANCOLLAS. J . Colloid Interface Sci. 52, 582 (1975). 20. M. C. CAFEand I. D. ROBB.J . Colloid Interface Sci. 86, 41 1 (1982). 21. F. V. WILLIAMS and R. A. RUEHRWEIN. J . Am. Chem. Soc. 79, 4898 (1957). 22. B. R. SMITH and A. E. ALEXANDER. J . Colloid Interface Sci. 34, 81 (1970). J. G. KNUDSEN, and R. W. MUELLER. COXO23. B. L. LIBUTTI, sion/84, National Association of Corrosion Engineers, Houston, Texas. Paper 179.