ANWENDUNG / APPLICATION Z. Amjad, Cleveland, Ohio/USA Performance of polymers as precipitation inhibitors for calcium phosphonate The influence of various polymers to inhibit the precipitation of calcium-hydroxyethylidine-I,/-diphosphonic acid (Ca- HEDP) from supersaturated solution has been studied at DH 75, 85, and 95 and temperatures ranging from 30 t0 70°C. The polymers studied include homopolymers of aerylic ‘acid, methacrylic acid, maleic acid, acrylamide, 2-acrylamido- 2methyl propane sulfonic acid. and acrylic acid-based copo- Iymers containing a variety of functional groups. It has been found that the addition of low levels of copolymer to the ‘supersaturated calcium phosphonate solution has a marked inhibitory effect on the precipitation of Ca-HEDP. The inhibi tion dara of several copolymers show that the performance of the copolymer sirongly depends on polymer compostion and molecular weight. Solution hardness, pH, and temperature also greatly affect the inhibitory power of the copolymers. Verschiedene Polymere wurden hinsichilich iltrer Wirksam- kel, die Palung von Colcivm-hydroxyethylidin-I.I-diphos phonsiusre (Ca-HEDP} aus tibersittigter Losung zw inkibie ven, bei pH 7.5, 8.5 und 9,5 und in Temperaturbereichen von 30-70°C untersucht. Die untersuchten Polymere waren Homopolymere der Acrylsaure, Methacrylsaure, Maleinsiure, ‘Acrylamid, 2-Acrylamido-2-methylpropansulfonsiure und Co- polymere auf Basis Acrylsdure mit verschiedenen funktionel- len Gruppen. Fs wurde deullich, daB die Zugabe geringer Mengen Copolymer zu der ubersittigten Ca-Phosphonat- losung die Fillang von Ca-HEDP vermindert. Der Vergleich mehrerer Copolymerer ergibs, daft die Wirksamkeit als Inhibi- tor stark von der Zusammenseizung des Polymers und dem Molekulargewiche abkangt. Wasserhirte, pH und Temperatur Deeinflussen die Wirksamkeit der Copolymeren ebenfalls stark 1 Introduction Phosphonates are a family of compounds widely used in a variety of applications in industrial processes such as water treatment, electroplating, paper and pulp slurries, scale femoval, crude oil production and pigment dispersion [1-3] ‘These organophosphonates differ structurally from polyphos- phonates in that they have a P-C bond rather than a P-O hhond. The structural differences account for their superior stability under extremes of pH and temperature. While many phosphonates are known, three of the most commonly used phosphonates in the water treatment formulations are ami notris (methylene phosphonic acid), AMP: hydroxyethylidine 1 .:diphosphonic acid, HEDP: and 2-phosphonobutane 1,24 tricarhoxylic acid, PBTC. ‘One of the attributes of phosphonates is their ability to inhibit the precipitation of scale forming salts (i.c., calcium carbonate, caleiumn fluoride, barium sulfate, calcium sulfate, 102 cte,) by “threshold treatment”. This term applies to the use of sub-stoichiometric levels (a few milligrams per liter, mg!) ‘of phosphonates to control precipitation of various scale forming salts Phosphonates are adsorbed onto crystal growth sites of subsmicroscopic crystallites, interfering with crystal ‘growth, and altering the morphology of those that grow. This, process can delay or prevent crystal growth. Phosphonates are also used to sequester metal ions such as copper, iron, manganese, and zine. Phosphonates are also effective in controlling mild steel corrosion. As corrosion inhibitors, phosphonates may gener ally be described as cathodic inhibitors. They function by reacting with calcium and other polyvalent metal ions, partic ularly those of the corrosion products. The phosphonate. cation products form a protective nonconductive layer on the ‘metal surfaces. This bartier separates the metal from the bulk water and prevents diffusion of oxygen to the metal sur- ace, thereby preventing corrosion. Phosphonates also exhibit some dispersaney activity towards deposits and a certain capacity to complex ferric ion. ‘While phosphonates are effective erystal growth inhibitors, dlispersants, and metal ion stabilizers, these compounds suffer from the disadvantage that under certain process conditions (Gc. high pH, high temperature, and high hardness) phospho- ‘nates ean react stoichiometrically with the calcium ion leading to a precipitation of calcium phosphonate. The calcium phos- pphonate salt can be a troublesome deposit by itself, but preci- pitation of ealeium phosponate from solution can deplete the solution concentration of phosphonate to such an extent that, severe caleium carbonate scaling can also occur. Recently, the precipitation of calcium phosphonate sealing in industrial water systems has become increasingly im- portant. Hogue [4] in his investigation of the precipitation of a number of phosphonates as a function of calcium ion con- centration and pH, reported that, under cooling water con: tions, phosphonates could form precipitates, presumably due to insoluble calcium phosphonate complex. Furthermore, AMP and HEDP were shown to exhibit about the same sus- ceptibilty to precipitation, Boffardi and Schweitzer [5] recog- nized that the relatively poor calcium tolerance of phospho- nates could be overcome by the addition of a copolymer of acrylic acid and sulfonic acid. Asherafi [6] studied the effects of temperature, pH, cal- cium hardness, phosphonate concentration, the presence of soluble iron, and the loss of phosphonate due to adsorption ‘onto Fe (I) sludge on the performance of HEDP. AMP and PBTC, These evaluations showed PBTC to be superior to AMP and HEDP under conditions of high hardness or pH, presumably due to the greater solubility of the Ca-PBTC salt ‘under harsh conditions ‘Smyk and Hoot [7] reported the influence of various poly- mers on the precipitation of calcium phosphonates. The results of this study show that acrylic acid based terpolymers, Carl Hanser Verlag, Miinchen Tenside Surf. Det. 34 (1997) 2Z. Amjad: Polymers as precipitation inhibitors perform better than homoaerylic acid polymers and copoly: ‘mers of acrylic acid and hydroxypropy! acrylate. In previous papers, we reported the effect of a variety of polymeric and non-polymeric inhibitors on the precipitation of a variety of scale forming salts including calcium phos- phate, calcium carbonate, calcium sulfate, barium sulfate and calcium fluoride [8-11]. Recently, the use of new acrylic ‘based copolymers in cooling and boiler water treatment applications as scale control agents and dispersants has increased significantly because of their excellent thermal sta- bility and superior overall performance in controlling the precipitation of calcium phosphates and also dispersing parti- ulate matter. Due to increased interest in the use of new copolymers, in this paper we present results of the efficacy of several copolymers containing a variety of functional groups Table 1. Polymers tested in preventing the precipitation of calcium phosphonate from ‘aqueous solutions. This paper also explores the role of water chomistry (Le., hardness, pH, temperature, etc.) on the per- formance of polymers for cooling water applications. 2 Experimental Grade A glassware and analytical grade chemicals were used, Stock solutions of caleium chloride solutions were pre- pared from calcium chloride dihydrate, filtered through 1022,m filter paper and analyzed by ion exchange and atomic absorption spectroscopy methods. The HEDP used in this study is a commercial material and the polymeric inhibi- tors used were selected from the range of experimental and commercial polymers. The polymer concentrations given in + CH CHa CH Cy I I Coon CHECOOCH: Tabor Stacie ‘ong Designation pobecyeacd) ECC. PAA ‘Commercial (K752) | coos polymakic acd) CHC PMA Experimental \ CoH Coon poly(metharyi sid) PMAA perimental polyacrylamide) PAM, Experiment polyacrylamide _4.CHECH Experimental Seashsl propane ee Psa, sulfone sd) a | NH \ cect \ GansosH poly(aegic acd 4.cti Ce CHC AADHPA Experimenta rds props : : sepia) ety \ Clie CH-CHOH polyacrylic aid: 2-acry-_{.CHy-CHbje-¢CHe CH CH) CHE ASA Tats pram i ‘ satis coon co @ NH sou \ cHh.CcH ( CHRSOH polyseslic cooct, AA:DMI Experimental Ted saimetyl isonste) im° 5 0S 20 2s [Poymen (mot) Fig 1. Ca-HEDP precipitation in the presence of verying fons of inhibitor (150 pom Ca. 13 ppm HEDP. pH 830, 30°C) this report are on dry polymer basis All polymers were tested under equal precipitation conditions, i.e. at the same supersaturation, temperature, and pHI of the solution. Some of the polymers were tested at different pH values. A Brink: ‘mann pH meter (model 632, Brinkmann Instruments, West: bury, New York) equipped with a pair of glass and calomel electrodes was used to measure pH. The electrode pair was calibrated before each set of measurements and checked afterwards against NBS standard buffers. ‘Supersaturated solutions of calcium phosphonate for pre- cipitation experiments were prepared by adding a known Volume of phosphonate (normally 10 to 20 ml) stock solution toa glass bottle (250 ml) thermostatted at constant terpera- ture, containing known volume of water. Following tempera- ture’ equilibration, the calcium stock solution was added in such amount that the final calcium concentration would be 150 mg/. Precipitation in these solutions was monitored by analyzing aliquots of the filtered (0.22 um) solution for phos. phonate concentration using the standard colorimetric method [8]. Experiments involving polymers were performed by adding the polymer solution to the phosphonate solution, before the addition of the calcium solution. The pH of the calcium phosphonate supersaturated solutions were adjusted to the required value using dilute solutions of sodium hydro- ide and/or hydrochloric acid Polymer efficacy as a calcium phosphonate inhibitor was calculated using the following equation: {lphosphonate|auslphosphonatehss) 9995 Inhibition (% 1) ce where Tphoxphonatelia = concentration of phosponate inthe filtrate in the presence ofiibitor at 20 hours [phosphonatehuae = concentration of phosphonate in te Bieate ia ‘he sbsence of inhibitor at 20 hours Iphosphonate}a) = concentration of phosphonate a the beginning ofthe experiment Table 1 lists the polymers evaluated in this study. 3 Results and discussion 3.1 Ca-HEDP inhibition by polymers 3.111 Effect of polymer dosage Results of precipitation experiments made in the presence of varying concentrations of AA:SA polymer (acrylic acid:2. acrylamido-2-methyl propane sulfonic acid) are summarized in Table 2, 104 Figure 1 (curve-1) shows the plots of % TI (threshold inhi bition) as a function of polymer concentration. The data clearly indicate that polymer dosage strongly affects the abil ity of the polymer to inhibit precipitation of calcium phos phonate. For example at a $ mg/l dosage, the AA:SA poly- ‘mer shows poor inhibitory activity (12% TH). However, at 410.0 mg/l, polymer performance is substantially improved (55% TD and at 20 mg/l, maximum inhibition is obtained, For comparison inhibition data for homo polyacrylic acid (PAA) is also illustrated in Figure 1 (curve-I1). The inhibition data on these polymers clearly show that under similar pre- Cipitation conditions, a copolymer of AA:SA outperforms PAA in controlling the precipitation of calcium phosphonate from aqueous solutions. It should be noted that similiar ‘dependence of performance behavior on polymer dosage has been reported in earlier studies of the precipitation of var- ious scale forming salts by polymeric threshold inhibitors 112-14}, Table 2 Inhibition data on Ca-HLEDP precipitation in the presence of olers Exper Polymer Cone pH TCC) TT iment (rel) 1 PAA sa) 2 PAK w 8B 3 PAA » 89 9 OB 4 MAA wo 80 5 PMA 850050 6 6 PAM 85050 2 7 PSA wo 85050 2 8 AASSA 5 80 9 AASSA 0 8 56 10 AASSA ne re | Ho AASA 20 8 DB 12 AAPA wo 70 1) AASHPA ssa 1M AASHPA nn a ed 15) AA:DMT was 10 6 AANBAM 10730 SOF 17 AARBAM = 10880 SD 1B AARBAM = 10980503 19 ASSA 0 78) ASA nS 21 ASA 930 8 2 ASA io 88) 23 ASSA mo 8508S 2% © AAHBAM 10830 28 AASBAM = 10850 260 AACHPA. 0 8s 8 27 AASHPA. 0 8 OB 28 ASSA 8s 5D 2 ASSA Se 30 AAHPA 83D 31 AASHPA, w 8 050 52 AASHPA. w 85050 33 AAPA a a 34 AAZHPA 1 850 50a 35 AASHPA. 85D 50 36 AASHIPA w 800m 50 my Ca, 15 mpi HEP. 20 bour © 75 mgl Ca, 15 ml HEDR, 20 hoar © 300 mg Ca, 15 mg/l HEDE, 20 hour molecular weight e108), 913-9) 9 1; 15,9 20 ‘Tenside Surf, Det. 34 (1997) 2Z. Amjad: Polymers as precipitation inhibitors 7 we -_ ° ° ze ze En ” fe Jo 60] Eso io 3 Ps Ff Ba iS 7 i = 6 $ 10 5 20 25 PMAA PAA PMA” PAM PSA AASA AAHFRAADIA ASA, Pater Fig 2. Ca-HEDP inhibition data for various homo- and copolymers (150 ppm Co, 15 ppm HEDP, pH 8.30, 30°C) 3.1.2 Effect of polymer composition For controlling the deposition of mineral scales such as CaCOs, CaS0y:2 H:0, BaSOs, CaF2, ete, and suspended matter on heat exchanger surfaces, various types of additives are used to achieve a variety of effects (e.g. scale inhibition, chelation, corrosion prevention, dispersaney, etc). Some commonly used additives include polyacrylic acid), PAA: poly(methacrylic acid), PMMA; poly(maleic acid), PMA: poly(acrylamide), PAM; and acrylicimalec-acid hascd co- polymers. Various types of bonding between the cations of the erystal surface and inhibitor molecule have been pro- posed. Many investigators have reported that the effective poly(carboxylates) with molecular weight between 1500 and 3600 only perform as scale inhibitors when in the given pH ange of functional acidic groups are partly deprotonated [15-17], Several studies on the influence of polymer composi: tion have shown [15, 18, 19] that both the monomer unit ratio and the type of functional group in the polymer exhibit 8 significant impact on the inhibitory power of the polymer in torms of controling the precipitation of scale forming salts In addition, Gill and Varsonik 20] reported that match: ing between acidic groups ofthe inhibitors and the cations at the crystal surface plays an important role in determining the effectiveness ofthe inhibitor. ‘The influence of the polymer composition was investi- gated for Ca-HEDP inhibition by @ series of experiments summarized in Table 2. The inhibition data shown in Figure 2 for a sumber of homopolymers (Le., PAA, PMAA, PMA, PAM, PSA, etc) reveal that whereas polymers which are devoid of carboryl groups (ie,, PAM and PSA) are ineffec tive as Ca-HEDP inhibitors, polymers that do contain carb oxyl groups (i, PAA, PMAA, PMA, etc) exhibit some inhibitory activity. For cxamplo, under similar experimental conditions, TI values obtained for carboxyl containing poly- mers are ~10 10 15% compared to <5% obtained for other homopolymers. This observation is consistent with earlier reports on these polymers regarding their performance in preventing the precipitation of calcium phosphate trom aqueous solution [ll]. ICis interesting to note that carboxyl containing polymers (.e., PAA, PMAA, etc.) which exhibit oor performance as CaHEDP and calcium phosphate in hibitors, have been shown to be effective inhibitors for other scales such as CaFz, CaSO4-2 HO and BaSOy, suggesting that carboxyl groups in the poiymer play an important role, perhaps by adsorption at the active sites ofthe growing crys. tals and preventing their growth [9, 10,18] The effect of substituting carboxy! groups with sterically bulky groups (ie, hydroxyl propyl acrylate, HPA; 2acryl ‘Tenside Surf. Det. 34 (1997) 2 Poe mesa weg (109) Fig. 3. Ca-HEDP precipitation inthe presence of AA:HPA copolymer Plots of threshold inhibition at a function of the polymer molecular weight (150 ppm Ca, 15 ppm HEDB, pil 850, 50°C) ido 2-methyl propane sulfonic acid, Sa; sulfonated styrene, ‘SS; dimethylitaconate, DMI; etc.) was evaluated for Ca- HEDP inhibition. Results shown in Table 2 and illustrated in Figure 2 clearly demonstrate that, compared to homo poly: ‘mers, the copolymers (i.c., AA:SA, AA:HPA, AA:DMI, etc.) show better performance as Ca-HEDP inhibitors. For ‘example, % TI values obtained for AA:HPA, AA:SA and ‘AA:DML copolymers at 10 me/l polymer concentration, pH 8.50, 50°C (expts 2, 9, 13, 15) are 48, 56 and 70% respec- tively, compared to 8% TI obtained for PAA. The marked improvement in the performance of various copolymers over PAA may be due to several factors including chelation abil- ity and adsoption and/or desorption characteristics of the Dulky comonomers to the growing Ca-HEDP nuclei, thus preventing the bulk precipitation of Ca-HEDP from aqucous solutions ‘The next polymer, in order of increasing effective. ness, is a terpolymer of acrylic acid, sulfonated styrene and sulfonic acid for A-SSA. Compared with PAA and AA:SA polymers, acrylic acid segments for A-SSA are partially sub- stituted by two sulfonic acid containing groups (i-e., SS and SA), thus significantly increasing the overal charge density. ‘The effectiveness of A-SSA as a Ca-HEDP inhibitor is sur- prisingly better than AA:SA polymer suggesting that both the overall ionic charge as well as the chain length or the bbulkiness of the comonomers play important roles in enhanc: ing the inhibitory power of the terpolymer over all the copo- Iymers evaluated. ‘The inhibiton data summarized in Table 2 and illustrated in Figure 2 suggest the following order of polymer effectiveness! A-SSA> AA:DMI> AA:SA> AASHPA, ‘The observed superior performance exhibited by the highly charged terpolymer for inhibiting Ca-HEDP precipi consistent with the results of a study [21] which showed that the best inhibitors for barium sulfate precipitation were those that imparted the most negative electrophoretic mobil- ity to the barium sulfate particles. Amjad [22, 23, 24) also reported similar observations in seeded growth studies of the effect of poly(carborylic acids) as crystal growth inhibitors for calcium carbonate, dicalcium phosphate dihydrate, and hydroxyapatite from aqueous solutions, 3.13 Effect of polymer molecular weight In recent years, many studies have been undertaken concern- ing the influence of molecular weight on the precipitation of seale forming salts. Studies of polymers as scale inhibitors have shown that polymer performance in industrial water 105Z. Amjad: Polymers as precipitation inhibitors a a i 90] A SSA 90 cad zor ee en ih 560] 2 60} Eo] is as is ce Bi BB EI souuion pt Fig. 4 Ca-HEDP precipitation in the presence of copolymers Plots of, threshold inhibition asa function of solion pH (130 ppm Ca, 13 ppm HEDP. 50°C, 10 ppm polymer) treatment applications is strongly affected by the polymer molecular weight. Smith and Alexander [25] reported that PAA was more cffective than PMAA in inhibiting the precipitation of cal- cium sulfate from supersaturated solutions Furthermore, growth inhibition results from series of experiments with Styrene/maleic anhydride copolymers suggest an optirium ‘molecular weight. Amjad, in studies on the influence of PAA in controlling. the precipitation CaSO.-2 HO, CaF and BaSO, from aqueous solutions, reported that the molecular Weight of PAA plays an important role in the inhibition of various scale forming salts (9,10, 18} Excellent examples of the molecular weight effects are provided by the A:HIPA copolymer. The threshold inhibition data for AA:HPA polymers, summarized in Table 2 and illu- strated in Figure 3, clearly shows that the higher molecular version of AA:HPA polymer exhibits significantly enhanced performance at 10 mg/l dosage, compared to the low molecu- lar weight version. The optimum performance obtained with polymer in the molecular weight range 10-15,000 for Ca- HEDP is coasistent with the results of eatlier investigations ‘on the inhibition of calcium phosphate by various copoly: mers [26,27]. 52 Influence of water chemistry on polymer performance 32.1 Effect of solution pH 1 is generally accepted that, increasing the cooling system HT has a two fold effect on system performance: (a) it tends to decrease the rates of metal corrosion, and (b) it inereases the scaling tendency by increasing the supersaturation of scale forming salts such as calcium phosphate, calcium earbo- nate, calcium phosphonates, etc. It is also well recognized that, for polymeric inhibitors such as poly(acrylic acid) and acrylic acid-based copolymers, the degree of deprotonation explains the observed improvement in polymer performance as the solution pH is increased from 4.5 to 9.0 (14, 28). In Fig. 4 tho Ca-HEDP inhibition for various polymers are ‘compared at a level of 10 mg/l at pH 75, 85 and 9.. As illu strated in Fig 4, at pH 7.5. A-SSA polymer showed 99% inhibition, while AA:SA polymer provided 73% inhibition, ‘As the pH{ was increased to 85, A-SSA polymer lost litle inhibitory power, while that of AA:SA polymer decreased. Figure 4 further ilustrates that increasing the pH from 8.5 to 955 resulted in only 5% drop compared to 75% provided by AA:SA polymer. From a practical point of view, an inerease 6f 050 10 1.0 pH units caused by system upset could have a catastrophic effect in the scaling of heat exchanger surfaces. 106 Solution ereparatre °C) Fig 5. Ca-HEDP preciptaion inthe presence of copolymers. Plos of ‘threshold inhibition asa faction of solution temperature (150 ppm Ca, 15 poms HEDP. pl 830, 10 ppm polymer) The incorporation of a high performance polymer such as ‘ASSA into the water treatment formulation will ensure bet- ter overall system performance. 2.2 Bifect of temperature It is well known that various factors such as water composi tion, total dissolved solids, pH, and temperature influence the solubility of scale forming salts. I s also generally recog. nized that the solubility of scalc forming sats such as calcium carbonate, calcium sulfates, and calcium phosphates are inversely dependent on solution temperature, The solubility temperature relationship suggests that the scaling tendency will be higher at the heat exchanger surface than in the other parts of the recitculating water system. Thus the ability of Ca-HEDP inhibiting polymers to exhibit excellent thermal stability under high temperature conditions and to provide superior performance under such stressed conditions is an important characteristic. ‘An effective Ca-HEDP inhibitor can brosden the operat ing parameters of a cooling water treatment program by maintaining HEDP in solution under conditions where it would otherwise precipitate Figure S shows the effect of temperature on the inhibition ‘of Ca-HEDP precipitation in the presence of several poly- mers. ‘The data in Figure 5 clearly demonstrate the superior- ity of the A-SSA polymer over the other polymers. At 30°C, A-SSA exhibits excellent efficacy while AA:SA is fair. ‘When increasing the solution temperature from 30 to 0 to 70°C, the A-SSA polymer retains most of its activity com- pared to AA:SS polymer. For example, whereas AA:SA polymer lost 75% activity, only 15% loss in activity was ‘observed in the case of A-SSA polymer. 323 Effect of solution hardness Recently, from a water conservation point of view, there has been an increasing trend in operating cooling water systems fat high cycles of concentration resulting in greater driving, force for the precipitation of scale forming salts. To over- ‘come this increased scaling potential a high performing poly- ‘met is required in the water treatment formulation in order to protect the heat exchanger from fouling. The tendency for Ca-HEDP precipitation increases with increasing caleium ion concentration. Another measure of the effectiveness of a Ca- HEDP inhibitor is its efficacy in igh hardness water. 1, the effect of the calcium hardness is demon- strated in low hardness (75 mg/l Car"), medium hardness (150 mg/l Ca-*), and high hardness (300 mg/l Ca") water. In low hardness water, the A-SSA. polymer provided excellent ‘Tenside Surf. Det. 34 (1997) 2Z. Amjad: Polymers as precipitation inhibitors 100 0 z% a) foo E50 40 axes Foo 0 ma °o wo 10160 00 250300 els hardness (a) Fig. 6 Effect of calcium hardness om she performance of polymers as CAHEDP inhibitors (18 ppm HEDP. nll £50, 30°C. 18 ppm poly. inhibition, whereas the AA:SA polymer performance was fair, In medium hardness water only A-SSA retained most of its activity, while AA:SA polymer was good to fair. In high hardness water, the AA:SA polymer shows decreased activ. jay, but the A-SSA polymer had substantially greater effi- ciency than the next most effective polymer. 4 Conclusions ‘The results presented in this paper support the following conclusions regarding the efficacy of homo and copolymers as Ca-HEDP inhibitors: f@ Homopolymers such as poly(aerylic acid), poly(meth- acrylic acid), poly(maleic acid), poly(ecrylamide) and poly(2-acrylamido-2-methyl propane sulfonic acid) ex! ‘poor performance as Ca-HEDP inhibitors ¢¢ Incorporation of bulky comonomers such as 2-hyéroxyl- propyl acrylate, sulfonated styrene, dimethyl itaconate and 2-acrylamide-2-methyl propane sulfonic acid in the polymer significanly inereases the inhibitory power of the polymer. ‘@ An increase in the copolymer concentration results in a Significant increase in the threshold inhibition @ The efficacy of the copolymers decreases with incre pH Gin the range of 7 to 95), temperature (in the range ‘of 30 to 70°C), and solution calcium hardness (in the range of 75 10 300 mg/l) References 1. Dequest Organophosphorus Compounds, Publication No, WT: ‘8603, Monsanto Chemical Compan, St Louis, MO. 2, Dubin, LI Cooking Tower Institute, 3 (1982) 17-22 Pee ae te Ralston, PH: ettol. Tech, 21 (1968) 1029-1038, Hogue, RR: “Sonsiiity of Dequest” Phosphonates to Elevated {sree of Calciom’, Report Ne B33, Monsanto Company. Sep tember 13, 1976 5. Bofforti BLP; Schweitzer, GW: Corrosion/85, Paper No. 132, [National Ascotiaton of Corrosion Engineers Heuston, TX, 185, 6, Ashoraf, RH: Comosions, Paper No. 128, National Assoc tion of Corrosion Engineers, Houston, TX. 1985 1. Svk, EF Hoows 1: Fivizant, KF; Fulks, K. 2: Corrosion! Bs, Paper No. 14 National Assciaion of Corrosion Engineers Huston, TX, 1988 8. Amjad, 2: Teside Sut. Det. 21 (1994) 12-17, 9, Amjad, Z. Langmuir, 7 (1991) 2405-2408, 10. Armiad, Z: Water Treatment, 9 (1938) 47-56, HL Amiad,Z: Colleids and Surfaces, 48 (1990) 95-106 12. Zuht, RW, Amjad, 2; Master, WF: Cooling Tower Institue, 8 (1987) 41 13. Hoong J Es Fvigzani, KF Cloud, RW: Corrsions9, Paper No. 175, Association of Corrosion Engineers, Houston, TX, 198. 14, Sih, B Re, Hui ¥; Water Treatment, 7 (1992) 51-66. 1S Imai, T; Uehuda, 7: Aho, S; Tauneks, 7: Corresion88, Paper No. 4223, National Association of Corrosion Engineers, Houston, TX, 198%, 16, Gnfith, D.W; Roberts § D- Paper No. 7862, International Sym: ppostum on Oilfield nd Geochemical Chemisty: Houston. TX, fons, 17, Libuth, BL Knudsen, LG Mueller R, Ws Corrosion 84, Paper No. 119, National Asociation of Corrosion Engineers, Houston, TX. 1984, 18 Amjad, Z. Con. J. Chem. 66 (1988) 1529-1536, 18, Piece, CC: Grasan "DA: CortesoaB8. Paper No. 205, National Association of Corrosion Enginoers, Houston, TX, 88 20. Gill, 1S; Varenik, RG 1 Coysal Grow, 76 (1886) 37-63 21, Coffey, M.D: Tate, Symp. Oileld, Paper SPE 53C2, Society of Petroleum Engineers Dallas, TX, 1973 2 Amjad, Z: Langme,3(1987) 234298 2 Amjad, Z: Chapter 1, pp. 1-11 in “Adsorption on and Susfoce Ghemisay of Hidroxjapatite", D'N. Mara (Ed) Plenum Pubr ishing Campany. New York, 1981, 24, Amjad, Zs Colloid Interface Sei, 117 (1987) 98-103 25. Smith BR Alevander, A. J Colloié Interface Se BL, 26, US Patent No. 4711-725. 27, US Patent No. 4366973, 28. Amind, Z Corcosion 8 Paper No, 178, National Assocation of ‘Corrosion Engineers, Houston, TX, 1588 34 (1970) ‘The author of this paper Zahid Amjad, Ph.D, ressved his M.Sc. in Chemisty ftom Pa Univesity and bis PD. in Physical Chemitcy from Glancow Une ‘erty He is eureatiy& Resear llow in the Avvanced Techno ‘gy Group of he BE Gonsch Company. His reat of research include water solubleswelsle polymers, adkorpion of polylscra ists at solduidincrnce, afd conto and Temoral of fouants ftom water iesiment apparitus-Dr_ Amjad holes 27 patents his futhored more than BS tehnest publications and us eed several tok He hax fen Inducted ino the National Hall of Conporate Inventors it Isted in mercan Men and Women of Science Who’ Who in Technology, and Who'e Who of Amertcan inventors, 0 i & somber of several profesional orgnatons ‘Gie60)