Characterization data of reference industrial polycarboxylate superplasticizer VP 2020/15.2 used for Priority Program DFG SPP 2005 "Opus Fluidum Futurum - Rheology of reactive, multiscale, multiphase construction materials".

An industrial polycarboxylate superplasticizer sample has been chosen in the Priority Program 2005 of the German Research Foundation (DFG SPP 2005). The molecular properties of this superplasticizer sample, such as molecular weight (Mw, Mn ), the polydispersity index (PDI) and the macromononmer conversion rate were determined using Size Exclusion Chromatography (SEC), and the sample's specific anionic charge amount was obtained via charge titration. Furthermore, the dispersing effectiveness of this superplasticizer sample was assessed through 'mini-slump' tests in pure OPC (CEM I 42.5 R) and in a limestone-calcined clay (LCC) cement. Moreover, the adsorption of the superplasticizer on both cements, and the dosage-dependent development of the zeta potential of both cement suspensions were captured. The data shall be used for the ongoing research within the Priority Program.

Impact of the drilling fluid system on the effectiveness of a high pressure jetting assisted rotary drilling system.

An enhanced drill bit combining high pressure fluid jetting with a conventional rotary drilling system incorporating a tailored drilling fluid was designed to improve drilling performance in hard crystalline rock. Full scale drilling experiments (8 ½ inch bit size) were performed utilizing a specially designed sepiolite fluid and comparing its performance with water and xanthan gum as a standard geothermal drilling fluid. The novel drilling system improved the rate of penetration by over 70% compared to the conventional drill bit without jetting assistance. In addition, the sepiolite drilling fluid retained its fluid properties even after high pressure jetting.

The effect of alginates on the hydration of calcium aluminate cement.

The hydration of calcium aluminate cement (CAC) in the presence of sodium alginate which is known to slightly retard Portland cement, was studied using heat flow calorimetry and mortar strength testing. Most surprisingly, addition of alginate resulted in an earlier occurrence of the maximal heat release as well as an increased early strength, thus confirming that in CAC alginate acts as accelerator. The thickening effect of alginate was effectively compensated using a superplasticizer while retaining its accelerating property. An investigation of the pore solution composition indicated that in the presence of alginate the concentration of calcium ions was reduced. Such effect normally causes retardation of cement hydration and should delay the formation of C-A-H phases. Apparently, the strong calcium ion complexing ability of alginate promotes the formation of C-A-H via e.g. a templating effect. A combined application of alginates and lithium salts presents a viable option to reduce the lithium consumption in CAC acceleration.

Adsorbed layer thickness of polycarboxylate and polyphosphate superplasticizers on polystyrene nanoparticles measured via dynamic light scattering.

HYPOTHESIS: Common superplasticizers (dispersants) for cementitious materials such as concrete include carboxylated comb polymers which strongly chelate Ca2+ ions. Thus, a substrate holding Ca2+ as docking site on its surface and of a narrow particle size distribution was expected to produce reliable values for the adsorbed layer thickness (ALT) of polycarboxylate comb polymers, as measured via dynamic light scattering. ALT presents a key parameter which controls the dispersion power of these polymers and provides the steric hindrance effect between cement particles. EXPERIMENTS: Using octadecyl phosphate as emulsifier, phosphate modified polystyrene nanoparticles (dH(z)~86 nm) of narrow size distribution were successfully synthesized and characterized via scanning electron microscopy, dynamic light scattering (DLS) and zeta potential measurements. The particles allowed to measure concentration dependent adsorbed layer thicknesses of a series of structurally different, self-synthesized polycarboxylate superplasticizers. FINDINGS: The phosphate-modified polystyrene nanoparticles were found to present a suitable substrate for ALT measurements of adsorbed polycarboxylate comb polymers. DLS measurements revealed that with progressing adsorption, these polymers develop a concentration-dependent isothermal ALT. At saturation point, layer thicknesses of 3 to 8 nm were observed. The values correlate well with molecular properties of the polymers whereby increasing side-chain length, side-chain density and molecular weight provoke higher ALTs.

A spectroscopic study of the complexation reaction of trivalent lanthanides with a synthetic acrylate based PCE-superplasticizer.

The interaction between different trivalent lanthanides and a synthetic acrylate based PCE-superplasticizer (52IPEG4.5) is investigated by using a combination of laser- and synchrotron based spectroscopic techniques. Time-resolved laser fluorescence spectroscopy (TRLFS) is used to obtain thermodynamic data (stability constants (log ß'(T)), reaction enthalpy (ΔrH) and entropy(ΔrS)) of the complexation reaction of Eu(III) and 52IPEG4.5 as a function of the temperature (20-80 °C) and ligand concentration (<2 g/kg) in 0.1 mol/kg NaCl solution. Under the chosen experimental conditions, the increase in temperature mainly affects the complexation properties (loading capacity) of the macromolecule itself rather than the stability constant of the formed complex (log ß'(T) ranging between 6.5 and 5.9). The thermodynamic results are complemented by extended X-ray absorption fine structure (EXAFS) spectroscopic measurements to resolve the molecular structure of 52IPEG4.5 complexes with Eu(III), Gd(III), and Tb(III). The results show, that each metal ion is coordinated by three carboxylic groups within the 52IPEG4.5 complexes. Furthermore, the determined interatomic distances exhibit that the functional groups are attached in a bidentate end-on fashion.

Adsorbed Conformations of PCE Superplasticizers in Cement Pore Solution Unraveled by Molecular Dynamics Simulations.

The conformations of polycarboxylate ether (PCE) type superplasticizer polymers adsorbed on the surface of MgO in cement pore solution are simulated by molecular dynamics (MD). Three types of PCEs commonly applied to concrete are simulated, namely a methacrylate type PCE (PCEM-P), an allyl ether type PCE (PCEA-P), and an isoprenyl ether type PCE (PCEI-P) with ethylene oxide (EO) unit numbers (P) of 25, 34 and 25, respectively. It is observed that the adsorbed layer thickness is inversely proportional to the experimentally measured adsorbed amount at the initial paste flow of 26 ± 0.5 cm. Simulation results indicate that the adsorbed layer thickness is sensitive to the initial polymer orientations against the model MgO surface. I.e., polymer molecules initially placed parallel/perpendicularly against the MgO surface gradually forms a train shaped or a loop and tail adsorption profile, respectively. As a result, the loop and tail shaped conformation gives a higher layer thickness.

A thermodynamical and structural study on the complexation of trivalent lanthanides with a polycarboxylate based concrete superplasticizer.

The complexation of trivalent lanthanides with a commercial polycarboxylate based concrete superplasticizer (Glenium® 51) is investigated using different spectroscopic techniques. Time-resolved laser fluorescence spectroscopy (TRLFS) in combination with a charge neutralization model is used to determine temperature dependent conditional stability constants (log ß'(T)) for the complexation of Eu(iii) with Glenium® 51 in 0.1 mol kg-1 NaCl solution in the temperature range of 20-90 °C. Only one complex species is observed, and log ß'(T) (given in kg per mol eq) shows a very slight increase with temperature from 7.5 to 7.9. The related conditional molar reaction enthalpy (ΔrH'm) and entropy (ΔrS'm) obtained using the Van't Hoff equation show that the complexation reaction is slightly endothermic and entropy driven. The thermodynamic investigations are complemented by structural data for complexes formed with Gd(iii) or Tb(iii) and Glenium® 51 using extended X-ray absorption fine structure (EXAFS) spectroscopy. The results imply a non-chelate coordination of the trivalent metals through approximately three carboxylic functions of the polycarboxylate comb polymer which are attached predominantly in a bidentate fashion to the lanthanide under the given experimental conditions.

Passive and active mechanical properties of biotemplated ceramics revisited.

Living nature and human technology apply different principles to create hard, strong and tough materials. In this review, we compare and discuss prominent aspects of these alternative strategies, and demonstrate for selected examples that nanoscale-precision biotemplating is able to produce uncommon mechanical properties as well as actuating behavior, resembling to some extent the properties of the original natural templates. We present and discuss mechanical testing data showing for the first time that nanometer-precision biotemplating can lead to porous ceramic materials with deformation characteristics commonly associated with either biological or highly advanced technical materials. We also review recent findings on the relation between hierarchical structuring and humidity-induced directional motion. Finally, we discuss to which extent the observed behavior is in agreement with previous results and theories on the mechanical properties of multiscale hierarchical materials, as well as studies of highly disperse technical materials, together with an outlook for further lines of investigation.

Impact of particle size on interaction forces between ettringite and dispersing comb-polymers in various electrolyte solutions.

The inter-particle forces play a fundamental role for the flow properties of a particle suspension in response to shear stresses. In concrete applications, cement admixtures based on comb-polymers like polycarboxylate-ether-based superplasticizer (PCE) are used to control the rheological behavior of the fresh mixtures, as it is negatively impacted by certain early hydration products, like the mineral ettringite. In this work, dispersion forces due to PCE were measured directly at the surface of ettringite crystals in different electrolyte solutions by the means of atomic force microscopy (AFM) applying spherical and sharp silicon dioxide tips. Results show an effective repulsion between ettringite surface and AFM tips for solutions above the IEP of ettringite (pH∼12) and significant attraction in solution at lower pH. The addition of polyelectrolytes in solution provides dispersion forces exclusively between the sharp tips (radius ≈ 10 nm) and the ettringite surface, whereas the polymer layer at the ettringite surface results to be unable to disperse large colloidal probes (radius ≈ 10 µm). A simple modeling of the inter-particle forces explains that, for large particles, the steric hindrance of the studied PCE molecules is not high enough to compensate for the Van der Waals and the attractive electrostatic contributions. Therefore, in cement suspensions the impact of ettringite on rheology is probably not only related to the particle charge, but also related to the involved particle sizes.

Interaction of cement model systems with superplasticizers investigated by atomic force microscopy, zeta potential, and adsorption measurements.

Polyelectrolyte-based dispersants are commonly used in a wide range of industrial applications to provide specific workability to colloidal suspensions. Their working mechanism is based on adsorption onto the surfaces of the suspended particles. The adsorbed polymer layer can exercise an electrostatic and/or a steric effect which is responsible for achieving dispersion. This study is focused on the dispersion forces induced by polycarboxylate ether-based superplasticizers (PCEs) commonly used in concrete. They are investigated by atomic force microscopy (AFM) applying standard silicon nitride tips exposed to solutions with different ionic compositions in a wet cell. Adsorption isotherms and zeta potential analysis were performed to characterize polymer displacement in the AFM system on nonreactive model substrates (quartz, mica, calcite, and magnesium oxide) in order to avoid the complexity of cement hydration products. The results show that PCE is strongly adsorbed by positively charged materials. This fact reveals that, being silicon nitride naturally positively charged, in most cases the superplasticizer adsorbs preferably on the silicon nitride tip than on the AFM substrate. However, the force-distance curves displayed repulsive interactions between tip and substrates even when polymer was poorly adsorbed on both. These observations allow us to conclude that the dispersion due to PCE strongly depends on the particle charge. It differs between colloids adsorbing and not adsorbing PCE, and leads to different forces acting between the particles.

Gram scale separation of casein proteins from whole casein on a Source 30Q anion-exchange resin column utilizing fast protein liquid chromatography (FPLC).

Casein is used as an additive in binders or paints and as such exhibits unique properties which might be based on the properties of certain subproteins in the complex whole casein mixture. Therefore, the separation of whole casein (CN) from cow milk was performed on a gram scale in order to yield sufficient amounts of the protein subfractions alpha-, beta-, and kappa-casein for further testing utilizing fast protein liquid chromatography (FPLC) and preceding enrichment in the case of kappa-casein. Construction chemical grade casein, which differs in quality from dairy grade casein, was used for separation because of our interest in the proteins responsible for plastification of cementitious systems such as mortar. The solubilized proteins were separated chromatographically via ion exchange chromatography (IEX) and the subsequently desalted protein fractions were tested for purity by isoelectric focusing (IEF).

Applications of biopolymers and other biotechnological products in building materials.

Bio admixtures are functional molecules used in building products to optimize material properties. They include natural or modified biopolymers, biotechnological and biodegradable products. Concrete and dry-mix mortars (e.g. wall plasters or tile adhesives) represent two major applications for bio admixtures. Examples of bio products used in concrete are lignosulfonate, sodium gluconate, pine root extract, protein hydrolysates and Welan gum; and in dry-mix mortar methyl hydroxypropyl cellulose, hydroxypropyl starch, guar gum, tartaric acid, casein, succinoglycan and Xanthan gum. In a number of applications, bio admixtures compete well with synthetic admixtures. Sometimes, they are indispensable in the formulation of certain building products. Their market share is expected to increase because of technological advances, particularly in the field of microbial biopolymers, and because of the growing trend to use naturally based or biodegradable products in building materials.

Retardation of setting of plaster of Paris by organic acids: understanding the mechanism through molecular modeling.

To develop an understanding of the action of specific formulations, the growth of gypsum crystals under the influence of retardation agents (tartaric and citric acid) has been studied using molecular modeling. Surface energies of gypsum and plaster crystal faces were calculated using established protocols. The crystal morphology predicted for gypsum crystals in the absence of retardation agents is in excellent agreement with experiment. The simulations show that only in an alkaline environment is the crystal morphology of gypsum changed by retardation agents. The simulations provide a detailed description of retardation, for example, the specific mechanisms by which tartaric and citric acid retard setting of gypsum and how they differ. At high pH meso, D(-), and L(+) tartaric acid inhibit both the growth of gypsum and the dissolution of plaster while at low pH tartaric acid and citric acid will principally inhibit the growth of gypsum. The simulations provide a molecular rationalization for a range of experimental observations and a basis for the selection of alternate retardation agents.