The working mechanism of carboxymethyl hydroxyethyl cellulose (CMHEC, Mw 2.6 x 10(5) g/mol) as fluid loss control additive (FLA) for oil well cement was investigated. First, characteristic properties of CMHEC such as anionic charge amount, intrinsic viscosity in cement pore solution, and static filtration properties of cement slurries containing CMHEC were determined at 27 degrees C and 70 bar. Effectiveness of the FLA was found to rely on reduction of cement filter cake permeability. Consequently, the working mechanism is ascribed to constriction of cement filter cake pores. Zeta potential measurements confirm that at low CMHEC dosages (00.3% by weight of cement, bwoc), adsorption of the polymer onto the surface of hydrating cement occurs. However, at dosages of 0.4% bwoc and higher, an associated polymer network is formed. This was evidenced by a strong increase in hydrodynamic diameter of solved CMHEC molecules, an exponential increase in viscosity and a noticeable reduction of surface tension. Thus, the working mechanism of CMHEC changes with dosage. At low dosages, adsorption presents the predominant mode of action, whereas above a threshold concentration of similar to 10 g/L (the overlapping concentration), formation of associated polymer networks is responsible for effectiveness of CMHEC. Addition of anionic polyelectrolytes (e.g., sulfonated melamine formaldehyde polycondensate, Mw 2.0 x 10(5) g/mol) to cement slurries containing CMHEC greatly improves fluid loss control. Apparently, the presence of such polyelectrolytes causes the formation of colloidal associates from CMHEC to occur at lower dosages. Through this mechanism, effectiveness of CMHEC as cement fluid loss additive is enhanced. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012