A mechanism study of chloride and sulfate effects on Hg reduction in sulfite solution

This paper studied the effects of sulfate and chloride ions on bivalent mercury (Hg²⁺) absorption and reduction behaviors in a simulated WFGD system. The aqueous mercuric ion-sulfite system reduction behaviors were monitored and investigated using a UV-visible spectrum. Thereafter, the mechanism of Hg²⁺ reduction in the presence of sulfate and chloride ions was proposed. Experimental results revealed that both sulfate and chloride ions had inhibition effects on aqueous Hg²⁺ reduction to Hg⁰. The inhibition was assumed due to the formation of (in the presence of ) and / (in the presence of Cl⁻). And it was found that complex was more stable than in excess of Cl⁻. The formation of the above-mentioned complexes in the presence of and Cl⁻ would damp the formation of HgSO₃, whose decomposition was assumed to be the key step of Hg²⁺ reduction.     

A greener, pressure intensified propylene epoxidation process with facile product separation

A novel biphasic process concept for the synthesis of propylene oxide (PO) from propylene is presented, using the long known catalyst, methyl trioxorhenium and aqueous hydrogen peroxide as the oxidant. Propylene is fed as gas, which is transported to the liquid phase containing the oxidant, catalyst and methanol as a cosolvent that improves propylene solubility. The selective oxidation produces PO which is distilled easily from the liquid phase taking advantage of the relatively low normal boiling point of PO compared to those of methanol and water. The process satisfies the sustainability principles of waste minimization, use of benign reagents and process intensification at mild conditions. The process produces PO in yields exceeding 98%. It operates at essentially ambient temperature and moderate pressures , using easily recyclable, low hazard aqueous methanol, as solvent. The catalyst, methyl trioxorhenium, is robust under the operating conditions. A key aspect of the innovation is the use of nitrogen gas pressure to enhance propylene availability in the liquid phase increasing its conversion from ∼80% (without N₂) to complete (with N₂) in a few hours. These findings pave the way for catalyst durability and recycle studies, aimed at demonstrating a continuous process that is economically and environmentally sustainable compared to existing processes.     

Numerical analysis on particle coating by the pulsed plasma process

The a-Si thin-film growth on particles in the rotating pulsed SiH₄ plasma process was analyzed numerically. The evolutions of chemical concentrations (SiH₄, SiH_x, and polymerized negative ions) in the pulsed plasmas have been shown during the plasma-on and -off. During plasma-on, SiH₄ is consumed by the electron impact dissociative reactions, but, during plasma-off, the disappearance reaction of SiH₄ stops because the electrons disappear in the plasma reactor. During plasma-on, SiH_x and are generated quickly by a fast dissociative reaction of SiH₄, but, during plasma-off, SiH_x disappears rapidly by a reaction with hydrogen and also by the deposition onto the reactor wall and particles, and is consumed quickly by fast neutralization reactions with the negative ions. The negative ions are polymerized by the reactions with SiH₄ during plasma-on, but, disappear by neutralization reactions during plasma-off. The growth rate of the film thickness profile depends on the SiH_x concentration because the particles grow with the SiH_x deposition. As the plasma-on time increases or as the plasma-off time decreases, the thin film thickness on the particles increases more quickly with faster SiH_x deposition onto them. A fraction of the particles falling down in the gas phase (W_FP) increases as the rotation speed of the plasma reactor increases. As W_FP increases, as the particle concentration decreases, or as the particle diameter decreases, the film thickness on the particles increases more quickly because the flux of SiH_x toward the particles increases.The pulsed plasma process can efficiently reduce the growth of polymerized negative ions and particles, both of which are not good for high-quality thin films. We showed that the high-quality thin films on the particles can be prepared successfully by deposition of low mass chemical precursors by pulsed plasma processes.     

Assessment of a redox alkaline/iron-chelate absorption process for the removal of dilute hydrogen sulfide in air emissions

The oxidative absorption of hydrogen sulfide (H₂S) into a solution of ferric chelate of trans-1,2- diaminocyclohexanetetraacetate (CDTA) was studied in a counter-current laboratory column randomly packed with 15 mm plastic Ralu rings. The present investigation takes concern about the Kraft pulping situation where dilute H₂S concentrations are omnipresent in large-volume gas effluents. A fractional two-level factorial approach was instigated to determine the significance of six operating variables, namely the solution's alkalinity (pH; 8.5-10.5), the liquid mass flow rate (L;1.73-), the solution's ionic strength (I_C;0.01-), the gas mass flow rate (G;0.19-), the inlet H₂S concentration (C_H2S,0;70-430 ppm) and the initial ferric CDTA concentration (C_Fe,0;100 -). Initially, a Plackett-Burman design matrix of seven duplicated experiments revealed that pH is the leading factor controlling the H₂S conversion rate while the ionic strength and ferric CDTA concentration effects remained negligible within the factorial domain. Surface response analysis based on 11 duplicated factorial experiments plus 10 central composite trials revealed that the H₂S conversion significantly increases with liquid flow rate but decreases with growing H₂S load up. Further examination about the influence of ferric CDTA on H₂S absorption rate was set up over a broader concentration range (C_Fe,0;0- at pH of 9.5 and 10.5. It showed good potential at as H₂S conversion increased by a significant 25% for both pH values in comparison to pure alkaline solutions containing no ferric CDTA.     

Kinetics of absorption of carbon dioxide into aqueous blends of 2-(1-piperazinyl)-ethylamine and N-methyldiethanolamine

The kinetics absorption of CO₂ into aqueous blends of 2-(1-piperazinyl)-ethylamine (PZEA) and N-methyldiethanolamine (MDEA) were studied at 303, 313, and 323 K using a wetted wall column absorber. The PZEA concentrations in the blends with MDEA varied from 0 to to see the effect of PZEA as an activator in the blends with two different total amine concentrations (1.0 and ). Based on the pseudo-first-order condition for the CO₂ absorption, the overall second-order reaction rate constants were determined from the kinetic measurements. The kinetic rate parameters were calculated and presented at each experimental condition.     

The effect of specific surface area on the activity of nano-scale ceria catalysts for methanol decomposition with and without steam at SOFC operating temperatures

Nano-particulate high surface area CeO₂ was found to have a useful methanol decomposition activity producing H₂, CO, CO₂, and a small amount of CH₄ without the presence of steam being required under solid oxide fuel cell temperatures, 700-1000 °C. The catalyst provides high resistance toward carbon deposition even when no steam is present in the feed. It was observed that the conversion of methanol was close to 100% at 850 °C, and no carbon deposition was detected from the temperature programmed oxidation measurement.The reactivity toward methanol decomposition for CeO₂ is due to the redox property of this material. During the decomposition process, the gas-solid reactions between the gaseous components, which are homogeneously generated from the methanol decomposition (i.e., CH₄, CO₂, CO, H₂O, and H₂), and the lattice oxygen on ceria surface take place. The reactions of adsorbed surface hydrocarbons with the lattice oxygen ( can produce synthesis gas (CO and H₂) and also prevent the formation of carbon species from hydrocarbons decomposition reaction (C_nH_m⇔nC+m/2H₂). V_O^·· denotes an oxygen vacancy with an effective charge 2⁺. Moreover, the formation of carbon via Boudouard reaction (2CO⇔CO₂+C) is also reduced by the gas-solid reaction of carbon monoxide with the lattice oxygen .At steady state, the rate of methanol decomposition over high surface area CeO₂ was considerably higher than that over low surface area CeO₂ due to the significantly higher oxygen storage capacity of high surface area CeO₂, which also results in the high resistance toward carbon deposition for this material. In particular, it was observed that the methanol decomposition rate is proportional to the methanol partial pressure but independent of the steam partial pressure at 700-800 °C. The addition of hydrogen to the inlet stream was found to have a significant inhibitory effect on the rate of methanol decomposition.     

Studies on comb-like polymer electrolyte with a nitrile group

The behavior of lithium ions in a comb-like polymer electrolyte with a nitrile group has been characterized by differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), ac impedance, Fourier transform infrared (FTIR) spectroscopy, and solid-state NMR measurements. The comb-like copolymer is synthesized by poly(ethylene glycol-methyl ether methacrylate) (PEGMEM) and acrylonitrile (AN). FTIR spectra reveal the interactions of Li⁺ ions with both the ether oxygen of the PEGMEM and the nitrogen atom of the AN segments. solid-state NMR spectra demonstrate the interactions of Li⁺ ions with both the ether oxygen of the PEGMEM and the nitrogen atom of the AN segments. Moreover, solid-state NMR shows that the lithium ions are preferentially coordinated to the PEGMEM segment. The T_g increases for the copolymers doped with LiClO₄. These results indicate the interactions of Li⁺ with both PEGMEM and AN segments form transient cross-links. The dependence of the maximum conductivity on the doping lithium ion concentration was determined. The AN unit in the copolymer improves the dissociation of the lithium salt, and the mechanical strength.     

The decrease of carbonation efficiency of CaO along calcination-carbonation cycles: Experiments and modelling

Successive calcination-carbonation cycles, using CaO as sorbent, have been performed either in a classical fixed bed reactor or using a thermogravimetric analyser. Significant differences in carbonation efficiencies were obtained, possibly due to different conditions prevailing for CaO sintering during the calcination stage. The effect of the presence of CO₂ on sintering was confirmed.A simple model of the decay of the carbonation capacity along cycles based on the specific surface area of non-sintered micrograins of CaO is able to predict the decrease of the extent of conversion obtained after 40 carbonations along calcination-carbonation cycles. The asymptotic extent of conversion is obtained when all the micrograins present within a grain are sintered. A detailed model of the carbonation shows that the voids present between the micrograins are filled up by carbonate when a critical thickness of the carbonate layer around each micrograin reaches 43 nm. Then, carbonation becomes controlled by diffusion at the scale of the whole grain, with the CO₂ diffusion coefficient decreasing (at ) from 2×10^-12 to as carbonation proceeds from 50% conversion to 76% (first cycle). This scale change for diffusion is responsible for the drastic decrease of the carbonation rate after the voids between micrograins are filled up.     

Intrinsic kinetics of the oxidative reaction of dichloroacetic acid employing hydrogen peroxide and ultraviolet radiation

In a previous work it has been shown that the combination of H₂O₂ and low wavelength UV radiation is a suitable process for degrading dichloroacetic acid (DCA). The final result provided a validated and complete reaction scheme. That proposal included two possible ways for the hydroxyl radical to react with DCA [Zalazar, C., Labas, M., Brandi, R., Cassano, A., 2007. Dichloroacetic acid degradation employing hydrogen peroxide and UV radiation. Chemosphere 66, 808-815].This work was directed to a single objective: to derive, from the previous reaction sequence, a mathematical model able to represent the kinetics of DCA oxidation and validate its predictive quality with experiments. This representation of the reaction must include all the required variables for an ulterior reactor design and scale-up and, consequently, the kinetic model parameters must be independent of the shape, size and configuration of the laboratory reactor.Working with a complete set of experimental runs that included all the involved variables, the unknown kinetics parameters of the DCA degradation were obtained by comparing predicted concentrations by the model (represented by a set of two ordinary differential equations and two algebraic equations coupled with a mass and a radiation balance inside the reactor) with the experimental values, employing a multi-parameter non-linear regression analysis. Experimental values confirmed the validity of the proposed mechanism. Additionally, an optimal concentration ratio of hydrogen peroxide with respect to DCA was obtained (r=CH₂O₂/C_DCA≈8).The intermediate results of the numerical solution of the complete system of differential and algebraic equations representing the proposed complete reaction mechanism were useful to find simplified, analytical expressions for the reaction rates of DCA and H₂O₂. The obtained rates resulting from these simplifications were compared with those of the complete system showing a very satisfactory concordance. This outcome is, at the same time, a clear indication of the significant influence of the radical in the reaction evolution.     

Systematics of salt precipitation in complexes of polyethylene oxide and alkali metal iodides

Conductivity measurements in PEO₃₀MI polymer electrolytes with M=Li, Na, K, Rb, or Cs over the temperature range from about 65 to 200 °C show an increasing tendency for salt precipitation with increasing cation size. The salt precipitation in these complexes upon heating is revealed by the decrease of the dc conductivity starting at a critical temperature T_c. Whereas LiI and NaI complexes do not show precipitation effects, T_c monotonically decreases from about 140 to 65 °C when changing the salt component from KI via RbI to CsI. For the PEO-RbI system, precipitation is further investigated by nuclear magnetic resonance (NMR) and tracer diffusion experiments. NMR analysis unambiguously demonstrates the onset of RbI salt precipitation and the increase of the precipitate fraction with increasing temperature. In diffusion experiments on PEO₃₀RbI with the radiotracers and , the precipitation effect is manifested by anomalous features in the penetration profiles, however, without noticeable changes in their depth range. Combining the resulting tracer diffusion coefficients with the dc conductivity data enables us to assess crucial parameters characterizing ionic transport in PEO₃₀RbI.     

Characterization of potassium glycinate for carbon dioxide absorption purposes

Aqueous solutions of potassium glycinate were characterized for carbon dioxide absorption purposes. Density and viscosity of these solutions, with concentrations ranging from 0.1 to 3 M, were determined at temperatures from 293 to 313 K. Diffusivity of CO₂ in solution was estimated applying the modified Stokes-Einstein relation. Solubilities of N₂O at the same temperatures and concentrations were measured and the ion specific parameter based on Schumpe's model was determined for the glycinate anion; the solubilities of CO₂ in these solutions were then computed.The reaction kinetics of CO₂ in the aqueous solution of potassium glycinate was determined at 293, 298 and 303 K using a stirred cell reactor. The results were interpreted using the DeCoursey equation for the calculation of the enhancement factor. The rate of absorption as a function of the temperature and solution concentration for the conditions studied was found to be given by the following expression:

     

Characterization of flow phenomena induced by ultrasonic horn

Mean flow and turbulence parameters have been measured using laser Doppler anemometer (LDA) in ultrasound reactor. The effects of the ultrasonic power have been investigated over a power density (P/V) range of 15-. The liquid circulation velocities are dominant in the zone nearer to the source of energy and are substantially low at the walls and at the bottom of the reactor. The levels of turbulence kinetic energy and dissipation rate are high near the horn and decrease rapidly with increasing distance from the horn. Average turbulent normal stresses are larger than the turbulent shear stresses. However, they are much lower than stirred reactors when compared at the same power consumption per unit mass. Comparisons of LDA measurements and computational fluid dynamics (CFD) predictions have been presented. The good agreement indicates the validity of the CFD model. The flow information has been extended for the prediction of mixing time. For uniform mixing in ultrasound-assisted reactors, optimum power density and diameter of the vessel is needed, yet it is far less effective than conventional stirred vessel. The possibility of optimization has been suggested in terms of power dissipation and the vessel size.     

Theoretical and experimental study on hydrodynamic characteristics of fluidization in air-sand conical beds

This work was aimed at modeling hydrodynamic characteristics of fluidization in conical beds using quartz sand as the inert bed material and air as the fluidizing agent. The minimum fluidization velocity, u_mf, and the minimum velocity of full fluidization, u_mff, were determined by Peng and Fan's models modified for conical fluidized bed. Meanwhile, the pressure drop across a bed, Δp (including Δp_max and Δp_mff corresponding to u_mf and u_mff, respectively), was predicted by using modified Ergun's equations for variable superficial air velocity at an air distributor, u₀. The predicted results were validated by experimental data for some operating conditions. Effects of the sand particle size, cone angle and static bed height on the fluidization pattern and hydrodynamic characteristics are discussed. With the proposed models, the Δp-u₀ diagram were obtained with rather high accuracy for the conical air-sand beds of 30-45^° cone angles and 20-30 cm static bed heights, when using 300- sand particles. For the predicted u_mf and u_mff, the relative computational errors were found to be within 20% for wide ranges of operating variables, whereas Δp_max and Δp_mff could be predicted with lower (10-15%) relative errors. With higher cone angles and/or bed heights, the computational accuracy was found to deteriorate.     

Formation and behavior of composite CO2 hydrate particles in a high-pressure water tunnel facility

Sinking CO₂ composite particles consisting of seawater, liquid CO₂, and CO₂ hydrate were produced by a coaxial flow injector fed with liquid CO₂ and artificial seawater. The particles were injected into a high-pressure water tunnel facility to permit determination of their settling velocities and dissolution rates. Injections were performed at fixed pressures approximately equivalent to 1200-m, 1500-m, and 1800-m depths and at temperatures varying from approximately 2 to 5 °C. Immediately after injection, the cylindrical particles were observed to break away from the injector tip and often aggregated into sinking clusters. The seawater flow in the tunnel was then adjusted in a countercurrent flow mode to suspend the particles in an observation window so that images of the particles could be recorded for later analysis. The flow would often break or cause rearrangement of some of the clusters. Selected individual particles and some clusters were studied until they became too hydrodynamically unstable to follow. In general, the flow required to suspend clusters or individual particles decreased with time as the particles dissolved. For example, one particle was produced and observed for over 6 min at an average pressure of 15.022 MPa and an average temperature of 5.1 °C. Its sinking rate, determined from the flow required for stabilization, changed from 37.2 to 3.3 mm/s over this time. Particle sinking rates were compared to correlations from the literature for uniform cylindrical objects. Reasonable agreement was observed for short times; however, the observed decrease in sinking velocity with time was greater than that predicted by the correlations for longer times. Particle dissolution rates, based on changes in diameter, were also determined and varied from 5 to . A pseudo-homogeneous mass transfer model was used to predict single-particle dissolution rates. Good agreement was achieved between experimental dissolution data and the modeling results.     

A modified model of computational mass transfer for distillation column

The computational mass transfer (CMT) model is composed of the basic differential mass transfer equation, closing with auxiliary equations, and the appropriate accompanying CFD formulation. In the present modified CMT model, the closing auxiliary equations [Liu, B.T., 2003. Study of a new mass transfer model of CFD and its application on distillation tray. Ph.D. Dissertation, Tianjin University, Tianjin, China; Sun, Z.M., Liu, B.T., Yuan, X.G., Liu, C.J., Yu, K.T., 2005. New turbulent model for computational mass transfer and its application to a commercial-scale distillation column. Industrial and Engineering Chemistry Research 44, 4427-4434] are further simplified for reducing the complication of computation. At the same time, the CFD formulation is also improved for better velocity field prediction. By this complex model, the turbulent mass transfer diffusivity, the three-dimensional velocity/concentration profiles and the efficiency of mass transfer equipment can be predicted simultaneously. To demonstrate the feasibility of the proposed simplified CMT model, simulation was made for distillation column, and the simulated results are compared with the experimental data taken from literatures. The predicted distribution of liquid velocity on a tray and the average mass transfer diffusivity are in reasonable agreement with the reported experimental measurement [Solari, R.B., Bell, R.L., 1986. Fluid flow patterns and velocity distribution on commercial-scale sieve trays. AI.Ch.E. Journal 32, 640-649; Cai, T.J., Chen, G.X., 2004. Liquid back-mixing on distillation trays. Industrial and Engineering Chemistry Research 43, 2590-2597]. In applying the modified model to a commercial scale distillation tray column, the predictions of the concentration at the outlet of each tray and the tray efficiency are satisfactorily confirmed by the published experimental data [Sakata, M., Yanagi, T., 1979. Performance of a commercial scale sieve tray. Institution of Chemical Engineers Symposium Series, vol. 56, pp. 3.2/21-3.2/34]. Furthermore, the validity of the present model is also shown by checking the computed results with a reported pilot-scale tray column [Garcia, J.A., Fair, J.R., 2000. A fundamental model for the prediction of distillation sieve tray efficiency. 1. Database development. Industrial and Engineering Chemistry Research 39, 1809-1817] in the bottom concentration and the overall tray efficiency under different operating conditions. The modified CMT model is expected to be useful in the design and analysis of distillation column.     

Enzyme kinetics of kinetic resolution of racemic ibuprofen ester using enzymatic membrane reactor

An ultrafiltration hollow fiber enzymatic membrane reactor was employed to study the kinetics of lipase-catalyzed kinetic resolution of racemic ibuprofen ester. Lipase from Candida rugosa was employed in the hydrolysis reaction both in free form in a batch system and in immobilized form in an enzymatic membrane reactor (EMR). The half life (t_1/2) of immobilized lipase on spongy layer was 105 h at reaction temperature of and 62 h at . This value was 94 h for lipase immobilized on the inner lumen and 45 h for free lipase in batch system at . Excessive substrate was found to inhibit the reaction as an uncompetitive inhibitor. The by-product 2-ethoxyethanol was found to be non-competitive inhibitor to the reaction when it was present in an excess. Michaelis constant (K_m) and maximum reaction rate (V_max) for immobilized lipase were and , respectively; and that for free lipase were and h^-1, respectively.     

Non-uniqueness in capillary pressure-saturation-relative permeability relationships for two-phase flow in porous media: Interplay between intensity and distribution of random micro-heterogeneities

The two-phase flow behaviour in porous media is determined on the basis of capillary pressure-saturation-relative permeability relationships (P^c-S-K_r). These relationships are highly non-linear and obtained by laboratory experiments on porous samples, typically around 10-12 cm in length. It is normally assumed that these samples are homogeneous; however it is well-known that this is in fact not the case and that even at this scale micro-scale heterogeneities exist. Two-phase flow experiments on soils with different properties (e.g., particle and pore size distribution, permeabilities, etc) result in different P^c-S-K_r relationships implying that they cause non-uniqueness in these curves. Recent work has shown that the presence of the micro-heterogeneities has a significant effect on the measured P^c-S-K_r relationships and they cause non-uniqueness in these relationships. In the previous work in this area, the micro-heterogeneity effects on the P^c-S-K_r relationships have been analysed in a number of contexts, e.g., uniformly distributed heterogeneities (simplified cases), various binary sand combinations, hydraulic parameters (e.g., entry pressure, permeability), boundary conditions, etc. There is also some evidence that the intensity and distribution of the micro-heterogeneities affect the P^c-S-K_r relationships. In the present work we use numerical simulations to investigate further the nature of these effects, in particular how the interplay between the intensity and random distribution of micro-heterogeneities affect the P^c-S-K_r relationships. Seven randomly heterogeneous patterns have been defined. These domains represent coarse sand media with fine sand blocks embedded in them. The domain size () has been chosen so that it represents a typical laboratory scale device. The results of the simulations show that it is particularly important to take into account both the intensity and distribution of heterogeneity when determining the effective P^c-S-K_r relationships of a sample. Further, there is a complex interplay between the intensity and distribution of micro-scale heterogeneities which determines the P^c-S-K_r curves. This observation is in contrast to the results of domains with uniformly distributed heterogeneities. We have found that in general if the intensity of heterogeneity is high; the irreducible wetting phase saturation (S_iw) of the sample is also high. The direction of flow and the orientation of the samples also have significant effects. For example, the injection of an immiscible phase from the top (vertically downward) of water saturated porous domain leads to a lower S_iw than injecting on horizontal plane. On the other hand, injection from the bottom (vertically upwards) leads to a higher S_iw. As expected, the distribution of heterogeneity has a significant effect on the saturation distribution and the shape of the P^c-S-K_r curves. However, we show that if the heterogeneities are distributed in such a way that they are closer to the boundary of injection, the irreducible wetting phase saturation is higher.     

The role of structural and electronic alterations on the lithium diffusion in LixCo0.5Ni0.5O2

The mechanisms for lithium diffusion in Li_xCo_0.5Ni_0.5O₂ were investigated using the galvanostatic intermittent titration technique (GITT). Membrane electrodes prepared with poly(vinylidene fluoride) and carbon black were employed in this study. The measured Brunauer-Emmett-Teller (BET) area of the Li_xCo_0.5Ni_0.5O₂ powder was combined with the GITT data to obtain the lithium chemical diffusion coefficient (), the lithium self-diffusion coefficient (D_Li⁺) and the thermodynamic factor (Φ) as a function of Li concentration (x). All three parameters vary non-monotonically with x. A minimum in and D_Li⁺ at x=0.5, along with structural changes, suggests the formation of a lithium superlattice at that concentration. The behavior of is complex but for x<0.34 it eventually undergoes a continuous decrease due to the metallic character of Li_xCo_0.5Ni_0.5O₂. We attribute the limitation of the specific reversible capacity of Li_xCo_0.5Ni_0.5O₂ to this decrease in and to elevated electrode voltages. Li transport in Li_xCo_0.5Ni_0.5O₂ is analyzed taking the variations in the cell parameters and the oxidation states of the Ni, Co and O ions into account.     

Fracture energy-fracture stress relationship for weak polymer-polymer interfaces

The bulk thick films of high-molecular-weight atactic polystyrene (PS) were brought into contact at a small contact pressure ≤0.2 MPa at a constant healing temperature T_h below the calorimetric glass transition temperature of the bulk . Fracture energy G and fracture stress σ of the auto-adhesive joints PS-PS were measured at ambient temperature in the T-peel test and the lap-shear joint geometry, respectively. In the framework of the diffusion controlled mechanism of the development of these two mechanical properties suggesting their evolution as and (t_h is the healing time), and as G∝1/T_h and σ∝1/T_h, a linear relationship between G^1/2 and σ, valid over a temperature range of , has been found. The penetration depth of 0.5 nm corresponding to the value of G calculated using the measured value of σ developed at for 24 h was reasonably smaller than the thickness of the surface mobile layer of 1 nm predicted by Wool's rigidity percolation theory for thick bulk PS films. The feasibility of a full healing of polymer-polymer interfaces below has been discussed. The dependence of an apparent activation energy characterising the process of segmental motions at PS surfaces and interfaces on the approach and the physical property chosen for its calculation has been analysed.