Cll and Surtaces i: hyscocom. Eng. Aspects 396 (2012)310-316 Content ists available ELSEVIER t SciVerse ScienceDirect Colloids and Surfaces A: Physicochemical and Engineering Aspects journal homepage: www.elsevier.com/l veolsurt Dispersion and rheological properties of ceramic suspensions using linear Polyacrylate copolymers with carboxylic groups as superplasticizer Bingyan Jiang», Shoufa Zhou», Hongguo ji », Bing Liao”, Hao Pang? {Key tatortory of Cellos nd Ligncells Chemistry, Guangzhou fae of Chemis, Chines cade of Scene uarezou 510880 Cina "Cram Schaolofthe Chinese endef Stace eg 10088 ch ARTICLE INFO ABSTRACT Received in ceised fom Accepted @ ana 2012 ‘vathbieonin 2 fnuany 2012 ‘To understand the relationship of molecule structure and dispersion mechanism, the Influence of near Dolycarbonylate-type superplasticizerson the adsorption properties nd rheological Behavior ofceramic Suspension were carved out in this study. Experiments, measuring the static and dynamic viscosity diferent polyelectrolytes and thei tnted in order to get wel-ispers ological behavior in concentrated ceramic slutty, were loves, Suspension with high slid content. The results othe viscosity "utes nccate thatthe ability of dispersing slurry manly depends on te amount of the charge dena Polyelectrolyte with more charge density led to better dispersing eilect. Meamuie ths leering pa easements were gest affcied by he sree dpe nn ont Fees ‘ined the mamieret poms argon and scene epee Men Se re scitcomalo atyaitecostaane abating mae tht eas he seo Shee more salesperson an hy in conzntated sttpcnaen, ee sony telaonsip between te pobmerdsage and iSong se se Contos ‘2012 Seer Ai ges reserved 1. Intreduction linear polycarboxyat-type SPs wl establish an equilibrium with With the increasing requirement of the ceramie products and ‘the rapid development ofthe ceramic industry the dispersion tech hiques in the ceramic siurry have been made large progress in the ceramic industry [1], This will result in developing kinds of addi. tives to get etter dispersion property and control the stability of ‘the system in order to gain high slid loadings and excellent luiity ‘of the slurry. itis well-known that polymeric dispersants, owning ‘well property of controlling the colloidal processing and keeping ‘z00d adsorption a the solid-liquid interfaces, are becoming more Popular today [24] ‘One of the most attractive dispersant s linear polyearboxylate- type superplastizers (SPs) with some active groups and shor side chains [5.6]. These dispersants have not only the advantage of polycarboxylate-type SPs, whose special chemical structures have the potential to be modified, and their freedom, molecular weight, Aistribution, active groups can be designed successfull, but they an supply effective electrostatic force between the particles own ing higher content of carboxylate anions and reduce the steric effect to Keep them good mobility in the system [7:8]. When adding ‘minor these dispersants into the slurry, the negative charge of * Govresponing autor Tel: +86 2085) 21226; fox +8620 852 3445. mal addres panghaoscac nH Pang 0927-77573 ~ se ont mater ©2012 Elev BV Al righ reserved 0:10 1016).cosueta 209201018 the ceramic particles, enhancing the stability and impeding parti cles aggregation by electrostatic interactions (9,10, and the paste will show a clear homogenous dispersion as well as keep high solid loadings and low viscosities, so that they can reduce the amount ‘of added water, save the energy requirements of the ceramic pro ‘essingand improve the quality ofthe final products [11] For these reasons, linear polycarboxylate SPs with unique characteristic of chain molecules have been introduced into ceramic systems to replacethe additives ike small dispersants and other types 1214, ‘The linear polycarboxylate-type SPs, especially polyacrylate salts including polyacrylate salts |15], polymethacrylates carry~ ing some carboxylic or sulfonic anions with ammonium cations [16] and terpolymers containing acrylic acid, acrylamide and vinyipyrrolidone [17], have been used in preparation concentrated ‘ceramic pastes, and they have significant effect on the dispersion and stability. I is widely accepted that interactions between the Gispersants and the particles are not only affected by the prop- erties of particles [18,18], but also by the chemical structure of the additives [20]. That is to say, the dispersing ability of addi tives depends on the electrostatic repulsion force andjorthe steric stabilization with the particles, even strongly being influenced by the hydrophobic/hydrophilic groups of the multifunctional dis. Persants, Some researchers have used kinds of polyacrylate salts as effective dispersing agents to control the stability and fluidity (of the ceramic slurries. The group of Marco found that whethergt a Clits nd Surfs: yoke ng Aspects 396 (2012) 310-316, sn in the mobility or stability, linear sodium polyacrylate is better than other polyacrylate dispersants, such as sodium poly(alky! sulfonate) [21], copolymer of sodium acrylate and sodium alkyl Sulfonated [16] and non-ionic poly(alkyl acrylate) (22) in raw poreelaingres. Romdhanea et al.compared the suspension stability ‘and rheological properties of «-Al,03 with adding ammonium salt St polymethacrylate and copolymer of sodium acrylate and vinyl {eate, found that copolymer with short side chains and multi- {groups had the good ability to sustain stable suspensions [23]. However there s noatteationon comparing the dispersion and fla- ldity effect of homopolyacrylate, copolyacrylate and multipolymer inthe raw porcelain gres, which bear same carboxylate anions and ‘odiim cattons. The main objectiveof this papers toinvestigate the “ispersion and theological properties of ceramic slurry with three different polyacrylate salts which have same anions but different ‘charge density. and a more effective dispersant for maximizing the Solid loading and controlling the stability of the suspension was found “To the best of our knowledge, this is the first report about comparing some linear-type polyacrylate salts with same anions, different charge density and molecular weight co investigate the felationshipof the chemical structure and the ability ofthe dispers- {ng and stability properties. We expect thatthe polyaerylate-type SPs with appropriate molecular weight and more charge density [eting as dispersant will have well dispersion and stability effets inthe ceramic sturry 2, Materials and methods 2.1, Materials: ‘The main chemical compositions of clay fume used in this paper (Foshan, China) are shown in Table I. The mean particle Size was 13.068 jm by using laser diffraction (Mastersizer 2000, ‘Malvern Instruments Inc, United Kingéom), and with about 50% tf the particles larger than 8919,m and the 100% of the clay particles were below 30.909 :m. The specific surface afea of the aw porcelain gres materials was 8.0339 m? g-', measured by the Brunauer-Emmet-Teller (BET) method though nitrogen adsorp. tion at 77K The isoelectric point (IEP) of these raw materials was at pH 90, determined by acid-base titration. ‘in order to evaluate the relationships between the polyelec- trolytes and adsorption ability as wel as the theological behavior in ceramic slurry, three different polyelectrolytes were added into the ceramic slurry in the present work, their corresponding informations are as follows: (1) a common linear homopoly- ‘mer of sodium acrylate (SA), having an ionized carboxylic group in each repeated unit, used as dispersing agents broadly in ceramic industry; (2) a copolymer of acrylic acid and maleic hydride (SAM) synthesizing by free radical polymerization, cat- fying some hydrophilic carboxylic anions: (3) mult-polymer of Soditim poly(aerylic acid-co-maleic anhydride-co-itaconic acid) (SAMI) owning more carboxylic groups in each unit and having larger molecular weight. The apparent molecular weights (Mn) of three polymers were determined at a 40°C witha gel permeation Chromatography (GPC) equipped with a Waters 717 autosampler, Waters 315 HPLC pump, ultra-hydrogel 250 columns, a Waters 22410 significant differential refractometer detector. NaC 0.1 mol/L ‘vas used as eluent at a flow rate 0.6mlmin, And the polymer charge density of the anionic charge density of polyelectroytes, {as measured by a Mitek PCD 03 PH (German) and 10 mL of sam- pie solution were filled into the measuring cell and titrated with 10.001 N polydadmacsolution. The physical and chemical structures ff these polyelectrolytes are summarized in Table 2 22, Polymer synthesis ‘The SA polymers were prepared by radical polymerization, according tothe classical method of conventional free radical poly ‘netization (24-261, The synthetic procedures of copolymer SAM “ind polymer SAMI were both synthesized by radical polymeriza~ tion of acrylic acid (AA), maleic anhydride (MA) oF itaconic acid {ia}, Polymer SAM was carried out in deionized water at 89°C {under the nitrogen atmosphere, with the ammonium persulfate land sodium bisulfite as redox initiators. Thereafter, the reaction rnixture was cooled, and the pH value was adjusted to 7 with Sodium hydroxide made the reactive system pH 7. The erude prod~ tueis were purified by anhydrous ethanol and acetone. Then the polymer was dried at 90°Cunder vacuum toa constant weight with ‘ost quantitative yields. SAMI: IR(KB) (wavenumber, cm |): 3435 (COW), 1735 (C=O), 2945 (CH). 1452 (CH), 1050 (C—O). "H NMR, '8(400 MHz, D20, TMS, ppm): 1.23 (~CH—CH-), 2.52 (CCH), 25-28 (-CH-C-,-CH-CH-, Cy). 23, Methods 23.1, Viscometric measurements “The steady state viscosity curves of concentrated mixed ceramic suspensions, as a function of dispersing agents dosage. were performed by a digital rotational viscometer (NDJ-8S. China) at 35" The suspensions prepared through adding 200. fine ceramic powder and 86g deionized water with different content of poly- lectrolytes, and then milled them effectively for Amin in a fast tniller machine. The total volume of the testing suspensions is TOOML and using NO.3 rotor with the rate of 6Dr/s to caleulate the stati viscosity ofthe systems 232. Zeta porental measurements ‘Adsorption of polyelectrolytes on ceramic particles was determined from the zeta potential measurements, using elec- trophoresis (Malvern Nano-2590 particle size analyzer, United Kingdom) at 25°C. A dilute ceramic slurry was prepared by 0.28 ‘of powder in 100ml deionized water. A total of 30 diferent poly tne solutions were prepared by adding three different dispersant tt ten different concentrations: 0, 50, 100, 200, 350. 500, 1000. 2000, 4000 and 6000mgL-. All suspensions were ultrasonic for ‘omin before testing. The Smoluchowski zeta potential (£) of the suspensions can be calculated by the dynamic mobility 233. Rheological measurements “The ceramic suspensions were prepared by mixing the ceramic powders, deionized waters and the dispersing azents, followed by milling 4 min in a fast miller machine to homogenize the suspen~ ‘Sion. After the systemstook’ htoreach adsorption equilibrium, the ‘obtained suspensions were put into a sealed flask for a day before theological testing, And the final pH of the slurry was around 8, ‘All suspensions contained 30% (w/w) of deionized water Different32. age a Calis nt supe: Pyscacer. Eng. Aspects 2962012} 310-316 able (Ghemiasrocture an properties of plylecteytes, Sodium aerate homopaymer(SA) iw saj=9500 = 4500 eas Sodium poty scr acd-o- maleic anhydride) (SAN) wr(SAM 1000 Poles charge deny (oH Sedum poly acy ai-co-malec any co-tacnic cd) (AM Mow (SaN-=13.00| Poymer charge density (p=) =6580 eas"! dispersants at 0.25% (w/w) on a dry weight basis were added into ‘the slurry to prepare different suspensions, ‘The rheological experiments were carried ou in a coaxial cylin der rotational rheometer with controlled shear rate (Brookfield RIS-CC, Germany) at25-+0.1°C.The rheological test consists ofthe following steps: (1) leaving suspensions stirring lonely at maxi ‘mum shear rate for 20min then standing for Smin: (2) a linear increasing of shear rate from 05" to the maximum shear rate for Smin (LS-HS); (3) sustaining the maximum shear rate for'S min to get the steady viscosity: (4) linearly decreasing the shear rate from the maximum shear rate to 05! (HS-15). Three maximum shear rates were 1005"* (5s of each point), 250s-1(12.5s of each Point). 500s-!(25s of each point), respectively. The parameters, ‘about shear rate. shear stress and viscosity were recorded on the computer. 234, Testing bending strength The ceramic suspensions were prepared like this: all samples containing 25% deionized water and 0.25% dispersants were added {nto the ceramic powders, and filled with alumina milling ballsin a 500 mt sintered corundum ceramic jar, then milled ata low speed for 10h, The ceramic bodies were prepared by the mold the length is 17.em and the width is 8 cm) of Foshan institute of Ceramic and after removing from the model, the sample the length is 13emand ‘he width is 2.5 cm) was kept one day at room temperature, and then dried at 70°C for 41 followed by 120°C for 4h. The breaking strength was tested by T2S-4000 breaking test machine of digi- tal ceramic tiles (Hangzhou, China), containing two down-bars for Supporting stent and an up-bar giving break force, The maximum testing force is 4000), the resolution is 1N and the relative ecror ist, 3. Results and discussion 3.1. Effect of dispersants on static viscosity of ceramic sturry with The static viscosities ofthe slurry foreach polymer at pH Increasing polymeric concentration are shown in Fig. 1 fou, e}- ‘As we can see from Fig. 1 that viscosities of the systems ini tially decrease with increasing the polymer amount, then start to Increase slowly with continuing adding additives into the suspen- sions. It also can be known from Fig. 1 that polymers have the ‘minimum viscosity as the dosage is increased to 0.3%. Moreover, the system with SAMI has the minimal viscosity values whieh decrease from polymer SA, SAM, SAMI, SA containing 00 low charge density and smallest molecular weight. This can be con- buted to the structure and charge density of polymer, fonized anionic carboxylic groups have a main responsible for decreasing ‘the viscosity by an electrostatic interaction with ceramic particles by controlling the effective charge density of paticle surface [22 ‘Based on the interaction mechanism of particles and the disper sants. the chemical characteristics including carboxylic equivalent or polymer charge density, molecular weight and structure should elucidate the relationship of concentration and viscosity, Poly- ‘mers with high carboxylicequivalentsand higher molecular weight lead to higher viscosity, and an excess of polymer wil lead to an Bee es “Te acing enount of pomersis) ig. let fhe dose of three dispersant an he visesity a eam sy SR. SAMC@) and Aa)[flan ta Cals nd Sra: Pycohem ng. Apes 396 (202) 310-316, a3 electrical double layer around particles 23}.The esultin Fig. indi tates the slurry with SAMI has a smaller viseosity than the others Sdding SA and SAM, because SAMI has proper molecular weight ‘and higher charge density in order to control the range of inter- particle interactions. Its likely that adsorption of some negative ‘charged flocculation agents onto the positive sites ofthe surface of, the particles can prevent the systems from forming ege-to-edge, tedge-to-face, of face-to-face structures, and result ina lower slurry viscosity in terms af good stability and flow properties [27 ‘When more than 0.4% of polymers SAM and SAMI were put into the slurry, the viscosities are prone to increase and reach aplatea ‘When adding excess additives into the slurry, the environment of ions willbe changed, and leading to compress the thickness of the diffusion layer, and even destroying electrical double layer caused by destabilization and flocculation in the concentrated suspen- sions. and further adding polymer into the suspension will increase the magnitude of the depletion forces, and lead to increase the tree polymer concentration inthe suspending system, so that floccula- tion and the viscosity ofthe suspension will increase finaly 4.2 Zeta potential eta potential, which isa functional of the surface charge of the particle reflects the effective charge on the particles and the elec- trostatic repulsion between them. Fig 2 shows the Smoluchowski zeta potential of ceramic particles for each adsorbed dispersant ‘with different concentrations. Tt-can be observed from Fig. 2 that over the whole range of the polymer concentration, the zeta potential values are negative Palmers concentra (met) Fie 2. Hf of th dosage ofeach polymer on zeta potenti of erami shy SA {sau} snasan ca) and indicating a strong negative charge on the surface of particles. Moreover, the negative magnitude ofthe zeta potential increases significantly as the dispersants gradually cover onto the surface ff the particles, and the values reach a saturation state. Itis more likely that the adding dispersants increase electrostatic repulsion ‘between particles. The polymer SAMI has the most significant effect ‘on the zeta potential with minor adding concentration. This ind fates that the amount of the charge density of dispersions can control the effective charge density of the particle surface and Shear sess P=) senses (Pa Shao) ig, shen ses (Ps) vrsashear ate (sor patil concentration with 03% ww fr each pole: SAW SAM (@)and SAMI) (2) ncesing of esate uD to bs": (b)ierssing Shear oteup 2304" and (inessng fea ate wp 005"1 nt tf nt gc = tats pee eet roa : ubett tues. Bis 1 Se i Bats “ is i: he lent compotion oh yt ary and te ha dens of the ates o wel se esting mats Compe ing the realopcal pres we kr the sen oh < pabmer Sa bang ge are ery and prone sig ame geo roi ar lower valu af vith san wth boner ea Fe. Seay tate vicoty at pate concentration 02% (5A m). SAM ani SAMI (a) forthe eee maxim shear tes tested (100250 500%) finally increase the electrostatic repulsion force [28,29}.The behav- ‘ris agreement with the viscosity research Fig. 1), which may infer that the sutface charge density, adsorbed by some polymers with some anionic carboxylic groups, will ead to form large electro stati repulsion between particles, which will prevent the ceramic Particles from agglomeration effectively, 33. Rheological properties ‘The plots of the shear stress versus shear rate from O5~! to the Gifferent maximum shear rates (100. 250, 5003-1) forthe tested Alispersing agents are shown in ig.3.And the following Fg. 4shows the steady state viscosity values forthe same maximum shear rates at 1005-', 2505-1, and 5005"! Its well-known that the rheological behavior of suspensions strongly depends on the types of dspersants and the shear rate. Asitcan be seen from Fig 3, polymer SAMI, as a better Nocculating agent. has the lowest shear stress and alow thixotropy, and the arca ‘of the thixotropy loop is smaller than others. all samples display 2 shear-thinning behavior seeing from Fig. 4 ‘Ascanbeseen from Fig. 3, the hysteretic area formed by upwards and downwards shear rates, and the time dependence behavior change over the shear rate, With increasing the maximum shear Tate, the hysteretic loops for three polyelectrolytes are becom- ing smaller and smaller, this may be caused by the shear-thinning ‘behavior and break-downing structure ofthe suspensions [30,31] ‘The hysteretic loop of polymer SAMIis the smallest one, this mainly depends onits higher charge density which will form clectrostati. effect to produce bigger repulsive forces and promote the motion of the particles. The number ofthe naked particles uncovered by the Polymersis less, the hystereticloop is smaller. Meanwhile, ncreas- ing the shear rate, the network ofthe system will be broken down, and lead to reduce the hysteretic loop. In addition, all suspensions show a classical positive thixotropy, For the concentrated ceramic slurries, they can be applied a power-law equation to compare the theological behavior deter- ‘mined by the nal colloidal suspension stability, which is expressed like this according to Yastida's equation [7.32]. nak a) ‘where isthe viscosity, n is the flow behavior index, and kis the consistency index which has alow value revealing lower viscosity when is identical, both of n and k set the equilibrium rheology. ‘Table 3 displays the rheological parameters. The values of n are Positive and the value is close with each ather, while the values ‘of parameter k have a great difference, This would be related to SAis exactly opposite. This means polymers SAMI have an excellent ability to reduce the viscosity and keep the suspensions more sta ble, and the viscosity is lowered in a more effective way when the polyelectrolyte has more chargedensity. This conclusion has a good Correspondence between the static viscosity and zeta potential. and itis consistent with the Marco" group [721 33} ‘The steady state viscosity ofthe ceramic suspensions atthe same shear rates was summarized in Fig. 4 The polymer SAMI has 3 lower viscosity than the other two (polymer SAM and SA). which hhas similar results with Fig. 1. This means that polymer SAML is, ‘more effective in improving fluidity at dynamic and static state. Moreover, according to the orders of electrical charge density of dispersing agents (Table 2), we know that the viscosity has a posi- tive relationship with the charge density. The dispersants bearing more charge density can adsorb on the particle surfaces effectively and form a strong barrier, which will reduce adhesion and agiglom- eration ofthe particles, and get a well-dispersed suspension with lower viscosity. 34, Bending strength test results According othe reference [34 the relationship of breaking strength andthe maximum lod of bdies can be expressed like oh sur AF 2 wiete is the breaking strength in MPa Fis the maximum load af odie in N, Lis the distance in mms the width in mm nd His the minimum thickness or the Iractre surface of sample in ‘nm, Measurements of the breaking strength wete made in five times, The results of bending strength experienced by the ceramic samples tthe moment at which he samples are crated ae given ings. According to Fi. 5a ofthe bending strengths Resty increase and then tedace withthe polymer conceniation. The bending strength of ceramic bodes wth polymers ae higher than the one without diperant, this means tha plyelectiatyte wil signi Gani reduce the water content ofthe srry as dispersant oF aterreducing agents, which i agreed withthe resis reported by Tokyayand Buyukyageet al [35.36} And also canbe observed trom fig. that when the same amount of dispersant arsed nto {he sry, the bodies contalning payne SAMI show the highest strength andthe values reach othe maximum value when adding 04% While the amount of ading polymer SAM is 0.3 the bendy Ingstrength sbigger than the one aading polymer SA These results ‘maybe analyzed from their diferent structures. The polymer SAMI has larger molecular weight and higher charge dent. The for- ter can make the long and wide backbones, which wil anchor nt the particles rmiyby electrostatic interactions Ad the ter ‘harge density. espedll owning nized COO wil chelate with‘jon eal / alo and Surface A Physcchem. Eng. Aspects 3962012) 310-316 ais ? : res i Seats eae er fe 5 sensing sensth of ceramic samples sing each spersant: SA (a), SAM (Siandsauicey the metal ions including AI", Fe?",Ca2*, Mg2*, which, will combine ‘with many water in the form of chelate compounds in the ceramic suspensions and release some bound water into thesystems, sothat fanteduce the adding water and then can decrease the ai contents. ‘when drying the bodies and reinforce the bending strength. "As can be concluded from the experimental results. there was a direct relationship between the viscosity of suspensions, the zeta potential and rheological property with the charge density of poly mers Alldatafrom Figs. 1-5 show thatincreasingthe concentration ‘of poiyelectroiyte can effectively gain concentrated and stability of, Suspension, and the polymer containing more charge density can Control the adhesion of the particles and polyelectrolyte. AS a con- sequence, it can be concluded that the electrostatic interactions ‘will have significant effect fr the fluidity and stability of ceramic suspension. 4, Conclusions {An investigation of the stability of ceramic suspensions. by adding three different polyacrylates bearing same anionic COO™ ‘with diferent charge density (SA. SAM and SAMI, was caried out to research their dispersion effect and rheological behavior. There isa close relationship between the viscosity ofthe system, the 2et3 potential and the rheology ofthe suspensions. And the main force keeping good adsorption and rheology depends on the molecular structure, charge density, molecular weight and the anchor groups. ‘And forthe linear polyacrylate-type SPs, the electrical interactions ‘seem to havea more important influence forthe fluidity and stabil- ity of the suspensions. The polymer SAMI with more charge density ‘and appropriate molecular weight has well-dispersed effect incon- ‘centrated ceramic suspensions and finaly get excelent rheological behavior and bending strength. Acknowledgments, ‘This work was supported by the cooperation project with Guangdong Province and Chinese Academy of Sciences (2009091100008) and Guangdong Natural Science Foundation (06200692) References [1] Pcolomio.c. Mera 8 Ride GD Sra, Folmer-devved ceramics: years Sreesearch and mova fo advanced crams, AM Cram. So (2010) 12) 5. outa, s pakou,C Pagnous, JF, Bumar, traction of cationic ae Sno alee with ty and lO, powders) Et cera. So (2602) [b] Ht ommer eration of plyarboateeter wits fume,. Eu Ceram, Se (2009) 1807-1853. [a1 Sk fonen © Peyatost, M, Crbelaud, A. Smith, JP. Sonnet, A. Jacque Ifuence oto operant on the Festi behavior asin and hte Irveonentted calm hydronic dispersions, AppL Ceram. Sc. 2008) dscns Is] Steer V tenet R.Sbrec, RV. 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