4-212

INTERFACIAL ENERGY IN THE LYOPHOBIC SYSTEMS AND

THERMOMOLECULAR ENERGETICS: СALLENGE TO ALL

PHYSICO-CHEMISTS Eroshenko V.A.

National Technical University of Ukraine, Kyiv Polytechnic Institute, Laboratory

of Thermomolecular Energetics, Prospect Peremogy 37, 03056 Kyiv, Ukraine.

E-mail: eroshenko@kpi.ua

Solid – liquid interface can store mechanical and thermal energy. The idea to

use this property in colloid lyophobic systems for effective energy storage, dissipation

and transformation is a basis of new area called “Thermomolecular energetics”

(TME), which develops rapidly today. New working media – heterogeneous

lyophobic system – consists of lyophobic porous matrix and non-wetting liquid.

In this paper the essence of new working media, brief review of its

characteristics development and examples of energy devises designed on their basis

are presented. The perspectives as well as scientific and technological problems which

must be solved to provide effective and rapid industrialization of the concepts of TME

aimed to increase energy and materials saving while improving ecological safety

indexes are discussed.

Introduction

Modern energy crisis demands not only development and exploration of new

energy sources (alternative, gas and oil, thermo-nuclear), but also efficient

transformation and storage of energy of existing ones, using not only conventional

gas/vapor, but in principle new working media.

In the search of physical and energy principles that could be the basis for new

working media originally all four fundamental forces were taken into account (strong,

weak, electromagnetic, gravity), but preference was given to the electromagnetic

forces [1]. The latter determine many of the physical properties and characteristics of

solids, liquids, gases and plasma, such as surface tension of the liquid for example.

The surface tension of the liquid (J/m2 or H/m) is the isothermal work of

development/reduction of unit of surface [2]. A remarkable feature of this

characteristic is that it characterizes the free (excess) energy per unit area (the latter

can perform useful mechanical work) and there is no thermodynamic restriction for

reversible “development – reduction” of the surface [3]. So the surface area is

related parameter of the surface tension [2], which defines Gibbs isothermal work of

surface development/reduction . Hence surface (or interface) can store and

release mechanical work, which is determined by the liquid nature ( ) and surface

area ( ). Gibbs also introduced the concept of isothermal heat of surface

development/reduction , where is temperature coefficient of

surface tension.

Naturally, Gibbs presentation of the surface energy immediately found wide

use, especially in colloidal and physical chemistry, where reactivity and kinetics of

the elements is largely determined by the value of the specific interface of the reacting

phases.

It is amazing that the "thermo-mechanical nature" of the internal surface energy

(heat + mechanical work) for almost two centuries, has not attracted the attention of

physicists and engineers, who preferred gas/vapor as working media for heat power

4-213

engineering. Perhaps one of the reasons of this fact is Gibbs-Helmholtz proof of

temperature invariance of the inner surface energy1 [4]. Apparently, the withdrawal of

the Gibbs-Helmholtz did not fit in the widely held belief of experts in the field of

energy: "If the internal energy of a physical substance (in this case - the surface) does

not depend on temperature, such substance can not be used for thermodynamic

transformations in heat engines" [5].

The idea that “non-wetting liquid + porous matrix” heterogeneous lyophobic

system (HLS) with huge specific interface (up to 1000 m2/gram of the matrix and

more) can be used as new working media with huge specific energy, was initially

proposed in the Soviet Union as a series of classified patents [1,6]. After these works

were partially unclassified and this idea achieved further development in many

countries, as a result a number of devices with unique characteristics were design and

constructed (see paragraph 3). It also stimulated an in-depth investigation of the

properties of "non-wetting liquid + porous matrix" heterogeneous lyophobic systems

(later also called repulsive clathrates [7-9]) in order to synthesize the HLS with

specified characteristics (often unattainable in the traditional engineering

thermodynamics). Positive results were achieved in the areas of porous materials

synthesis and modification [10–21], the mechanism of the matrix defects formation

during HLS operation [22–24], HLS thermodynamic and thermophysical

characteristics [9,24–39], percolation effects in HLS [40, 41], characteristics of HLS

based on electrolytes [42–45], molecular dynamics [22, 46–50], HLS characteristics

for energy storage and energy conversion [25, 32, 51–61], the use of HLS for energy

dissipation [51,58, 62–72] and other devices and processes [8, 45, 51, 56, 73–75].

From the above it can be seen that a new direction "Thermomolecular energy2”

(TME) [76,77], aimed to investigate HLS properties for efficient energy conversion,

storage and dissipation, is interdisciplinary and requires an integrated approach based

on the knowledge from the areas of physical chemistry, thermodynamics of surface

phenomena, molecular physics, the theory of capillarity, hydraulics, etc.

Fundamental differences of the HLS properties and characteristics, in

comparison with conventional working mediums (gas / vapor), is primarily a result of

the fact that HLS is a condensed system (phase transitions of liquid-vapor are absent

or play a minor role) in which dominant energy is the potential energy of

intermolecular interactions at the “solid – liquid” interface, while for gas / vapor it is

kinetic energy of particles thermal (chaotic) motion in the volume phase. The

relevance and rapid development of fundamental and applied works in the field of

TME is also confirmed by a statement that modern heat engines and thermal power

plants using gas / vapor has practically reached the limit of its thermodynamic

perfection and it is unlikely to expect a significant improvement of their performance

in the near future.

In this paper it is demonstrated how the fundamental differences of new

working media can provide nonstandard design solutions, and at the same time bring

new interdisciplinary challenges to improve the characteristics of the HLS-based

devices and power systems.

1 Only for liquids with non-linear temperature dependence of the surface tension inner surface energy

may depend on the temperature. Yet for most liquids surface tension temperature dependence is close to linear. 2 “Thermomolecular” term indicates the dominant role of intermolecular forces in a heterogeneous

lyophobic system which are temperature dependent

4-214

1. The essence of new working media

Physical realization of new working media is the following (fig.1): "non-wetting

liquid + solid porous matrix in the form of powder" is placed inside the "cylinder-

piston" working chamber. System is lyophobic (contact angle of the liquid on the

border with solid , which eliminates penetration of the liquid into the pores of

the matrix under ambient pressure and temperature (initial conditions). If the pressure

in the system increases to a certain threshold (for example, an external force applied

to the piston) the liquid penetrates into the pores of the matrix, which is accompanied

by the development of the huge specific interface , the decrease of system volume

and the accumulation of mechanical energy (where is

the volume of the pores) [1]. The threshold pressure under which intrusion of the

liquid into the pores takes place is determined by Laplace capillary pressure (in the

form of Washburn [78]):

where advancing contact angle corresponds to intrusion pressure , and receding

contact angle corresponds to extrusion pressure , is the pores radius

(cylinders are considered in eq. (1)).

Now if the pressure in the system decreases to a pressure of , self-driven

extrusion of the liquid takes place, which corresponds to a reduction of interface of

the system, its volume increase and the release of mechanical energy, i.e. performed

work . Observed hysteresis in

compression-decompression cycle can be either rather small (curve 1 in Figure 2) or

quite large (curve 2) up to 100% (curve 3).

4-215

Fig. 1. Heterogeneous lyophobic system on the different scales during

compression (a) and decompression (b).

It can be seen from figure 1 that the dimension of the space of the system acts as

its thermodynamic potential [6, 79]: a steady transition from 3D working liquid, with

its initial volume (see Fig. 1a) to 2D interface and sometimes to 1D molecular chain

(for example, a one-dimensional chain of water molecules in the pores of zeolites with

pores radii of about 3Å [16, 17, 22–24, 34, 52,53, 57]) corresponds to the

accumulation of energy in the system, while dimension increase from 1D to 3D (see

Fig. 1b, extrusion of fluid from the matrix) corresponds to the release of accumulated

energy of the system.

HLS with minimum hysteresis (3 – 5% for modern samples [52, 53, 59]) are

used for energy storage and convertion [6, 52, 53, 61], while HLS with large

hysteresis are suitable for effective energy dissipation [11, 65–72].

The nature of indicated hysteresis H is a separate issue and is beyond the scope

of this article.

Fig. 2. Heterogeneous lyophobic systems with different values of hysteresis in

the compression-decompression cycle: curve 1 – minimum hysteresis, 2 – large

hysteresis, 3 – 100% hysteresis.

It is important to note that the development / reduction of the interface is

accompanied by thermal effect [25, 26], which has been demonstrated for HLS

experimentally [23, 31, 80]. The compression process (interface development) is

accompanied by an endothermic effect and the decompression process by exothermic

one. That means that the compression process of HLS requires not only the work

(2), but also the heat (3) to be supplied to the system.

4-216

Module in eq. (2) indicates that the negative value of the cosine already

taken into account. The value of is a function of the volume variation and the pore

radius , as the HLS volume variation is determined by the interface area

development ( [11, 25, 27]), and by the liquid ( ) and the matrix ( )

volumes variations due to forced or thermal deformation:

is a pore geometry coefficient (for long cylinders , for spheres ),

.

Eqs. (2) and (3) and also linear temperature dependence of surface tension (for

simple liquids [2]), allow to obtain useful relation [5,31]:

where and is the critical temperature of the liquid.

Fig.3. Relation between work and heat of isothermal interface development for

HLS as a function of temperature [5].

Graphical representation of eq. (5) is presented on the fig. 3. It can be seen that

the HLS compression-decompression under low temperatures is mostly

followed by accumulation and release of mechanical work ; while

4-217

under high temperatures HLS compression-decompression is

mostly followed by accumulation and release of heat ; if the

accumulation and release of mechanical and thermal energy takes place with equal

amounts (i.e. ) [5].

2. Relevant issues and recent developments in thermomolecular energetics

As can be seen from the nature of heterogeneous lyophobic system described

above, most important parameters that determine its ability to store and convert

mechanical and thermal energy are the values of the specific interfacial area and

temperature derivative in equation (3).

Achieving maximum value of is associated with the search for the optimum

in technological problem: the unreasonable increase in porosity leads to a decrease in

the mechanical strength of the matrix frame. For a given porosity maximum

interface area is achieved with a minimum radius of its pores (with a maximum

working pressure , according to (1)). Specific energy of HLS (J/m3) can be

expressed as [81]:

is the matrix porosity, is interparticle porosity.

Equation (6) shows simple practical recommendation: to increase the specific

energy of HLS matrix porosity must be increased as well as its working pressure,

while interparticle porosity should be decreased.

The value of is rather complex issue as there is no single theoretical

approach to determine and , which makes it difficult to predict these quantities on

the basis of the characteristics of the fluid and the matrix.

Despite the large number of works aimed at the study of the surface tension, the

problem of synthesis of liquid with a given surface tension temperature coefficient is

still topical for many areas of science and engineering [82–84] including the creation

of the HLS applicable for a new class of heat engines [73].

Silica gels, zeolites, aluminum silicates, porous glasses and many other

materials with highly developed specific surface area (from 100 to 1000 and more

m2/g) may be used as matrix for HLS. The working liquid may be water and aqueous

solutions, melted salts and metals, or low temperature eutectic alloys.

The most successful class of matrices for HLS used in the processes of energy

storage and conversion are superhydrophobic zeolites [52, 53, 59]. HLS based on

indicated matrices and water usually has negligible hysteresis, therefore, despite the

relatively small volume of the pore space of these matrices, they can be used to store

large amounts of energy. Significant progress in the search for and synthesis of high-

quality superhydrophobic zeolites with the necessary characteristics has been done by

Patarin and co-workers [19, 23, 59, 60]. Among the large number of different porous

matrices, including such as silicalite-1 (MFI-structure type) [23, 52, 53, 59], ZSM-5

(MFI) [32, 42], SSZ -24 (AFI) [59], silicalite-2 (MEL) [59], ZSM-22 (TON) [59],

ZSM-12 (MTW) [59], there are some remarkable samples as ferrierite, which coupled

with water can store up to 15 J / g (gram of the matrix with) with a hysteresis of only

~ 3% [59]. The drawbacks to be removed, should include the small pore volume and

4-218

high operating pressures (~ 100 MPa) in the indicated HLS, which limits their use. A

fine example of high energy (13.3 J / g) and thus acceptable operating pressure (27

MPa) HLS is a metal-organic framework ZIF-8, tested recently in a pair with water

[60].

To achieve HLS with stable characteristics matrices with a defect-free structures

must be used, the quality of the matrix should also prevent the formation of defects

during operation process (numerous cycling), as experiments show that indicated

defects can greatly distort the operating characteristic of the HLS [23, 24].

The heterogeneous lyophobic systems used in the processes of energy

dissipation [65–72] have a significant pressure hysteresis (of about 85-90%) during

the compression-decompression cycle (Fig. 2, curve 2). For example, a typical value

of dissipated energy per one cycle for HLS based on "hydrophobized silica gel +

water" is about 12 J / g [68, 70]. The system shows high performance stability (up to

10 million cycles of full compression-decompression [69]) and the ability to operate

at frequencies beyond the reach of conventional hydraulic shock absorbers [35, 58,

68]. Experiments were performed at frequencies up to 20 Hz [35] and up to 22 Hz

[68], wherein the theoretical calculations indicate the possibility of HLS to operate at

even higher frequencies. That of course is to be confirmed experimentally.

Even more significant value of dissipated energy were obtained by Qiao et al.

Using HLS based on the same matrix with mercury as working fluid, 41 J / g of

mechanical energy were dissipated under dynamic crush with 100% hysteresis

(irreversible intrusion, see curve 3 on the Fig. 2) [66].

The above described characteristics certainly found their realization in the field

of power equipment.

3. Examples of devices based on heterogeneous lyophobic systems

3.1 Self-contained actuator for space applications

The large specific energy density of heterogeneous lyophobic systems (HLS)

allowed to construct a compact device for deploying solar panels and operating

optical instruments on satellites and spacecrafts (Fig. 4) [51].

The actuator is presented by "cylinder – piston with the rod" system. The

working chamber is filled with HLS in the pre-compressed state (liquid fills the pore

space of the matrix, the rod is placed on the electromagnetic lock). By a signal from

the earth the lock is removed and HLS discharge takes place (fluid extrudes from the

pore space of the matrix and moves the rod) and device performs useful work. With

the volume of the working fluid of about 15 cm3 and the specific energy of 6 J/cm

3

( , ) actuator performed a displacement of 100 mm with a

constant force of 800 N. As a result four times lighter device based on heterogeneous

working medium has provided force twice as high as conventional analogue based on

the application of 13–15 "cleverly" connected Hooke type springs.

4-219

Fig. 4. Self-contained actuator based on heterogeneous lyophobic system.

3.2 Car shock absorber

The presence of a significant hysteresis in the compression-decompression cycle

of HLS based on water and hydrophobized mesoporous silica, as well as the ability of

this system to operate at high frequencies, allows to create an effective shock

absorbers (fig. 5). The shock absorber device of a new class and its operating

principle can be found elsewhere [64, 67–72].

Shock absorbers based on the HLS/RCs have unique properties to operate in

domains inaccessible for classical analogues under frequencies up to 22 Hz for

mechanical rods amplitude fluctuations of 0-80 mm [67, 68]. Recently Suciu and co-

workers have experimentally demonstrated the stability of such devices after 10

million cycles of full compression/decompression, which agrees with the life of

general machine elements [69]. While the specific power of energy dissipation

through the new shock absorber (20–50 W/cm3) is much higher compared to

conventional (oil) analogue (0.10-0.15 W/cm3) [68], wherein ride-comfort of such

shock absorber meets indices of traditional commercial analogues [72].

4-220

Fig. 5. Car shock-absorber based on heterogeneous lyophobic system [67, 68].

This new shock absorber dissipates the energy of external mechanical

perturbation with only 15 cm3 of the working heterogeneous medium {hydrophobic

silica gel + water}, while a traditional damper requires 1500 cm3 of the technical oil.

It is remarkable that about 100 million shock absorbers filled with oil could be phased

out of exploitation each year worldwide avoiding therefore huge recycling.

3.3 Thermal lock

The essence of the smart autonomic compact device (fig. 6) is the following.

Under temperature higher than the temperature of the alloy crystallization , an

alloy (or an eutectic) with a set down melting point is pumped through a pair of

pistons and rods into the matrix pore space and under compressed state is cooled

down to the environmental temperature. Under such conditions the alloy solidifies and

remains in the matrix as long as its temperature is lower than . As soon as the room

temperature rises to the melting point of the alloy, it will liquefy and under the

capillary pressure will be thrown out from the matrix pore space. In such way the

piston displacement may relieve the cooling agent (e.g. water or foam) to eliminate

the source of overheating. Such “thermal lock” is fully autonomous and does not

require any additional sensors or sophisticated mechanisms [51]. For example

constructed sample with weight of only 600 g performed a constant force of 2000 N.

4-221

Fig. 6. “Thermal” key based on heterogeneous lyophobic system [51].

The above described system is successfully employed to create the thermal

sensitive trigger device to be used in the field of nuclear energy [74], namely for the

emergency protection systems of the nuclear reactors from the overshooting of the

security temperature level. It also can be used to protect the chemical, technological

and other energy equipment as regards their temperature level [74].

3.4 A new thermodynamic cycle

It has been proposed to use HLS/RCs in new thermodynamic cycles and

Thermomolecular engines, with , where is the Carnot efficiency,

and thermodynamic compactness 10–100 times higher than for conventional heat

engines and refrigerators (without the need of ammonia and Freons). A detailed

theoretical description of the working cycles and heat engines can be found elsewhere

[6, 73]. Below a brief description is given of the thermodynamic cycle involving a

simple rigid pore and a liquid cluster forming a repulsive clathrate (RC), see Fig. 7,

along four steps (strokes I to IV).

At the initial stroke, Stroke I, the nanopore 1 and the liquid cluster 2 have a

temperature of the cold source . The internal system pressure is less than the

intrusion pressure which is necessary for cluster 2 to penetrate inside nanopore 1.

Next, the nanopore 1 and liquid cluster 2 are heated up to the high temperature region

. Since liquid 2 and the pore 1 are assumed incompressible, their heating due

to the external heat of the hot source (where is the total

heat capacity of the bulk phase liquid and matrix framework) can be considered as

4-222

isochoric and isosurface . The heat capacity change

during the heating process from to is neglected.

At the second Stroke II, under temperature, the intrusion pressure of the pore

decreases according to eq. (1) until it reaches the value. In this case, the liquid

cluster 2 can be easily intruded into the nanopore 1 at a low pressure , hence the

mechanical work of the interface area development is done

over the system according to equation (2).

As already was mentioned above, the formation process of the interface area is

endothermic, therefore one should supply the system with the heat of interface area

development under the isobaric-isothermal conditions according to eq. (3)

During the third stroke, Stroke III, which occurs at a constant volume and

interface area, the working medium is cooling down to due to removal of the

heat from the system to the cold source. At the end of the third stroke the

extrusion pressure increases to the initial value due to temperature decreasing and

surface tension increasing.

Fig. 7. New thermodynamic cycle for heterogeneous lyophobic system [73].

At the forth Stroke IV, by virtue of the increased capillary pressure the liquid

cluster 2 is pushed out of pore space 1. The isobaric-isothermal reversible reduction of

the interface area between liquid and solid phase takes place

. During this process the heat of the area reduction is

released and removed to ensure isothermality of the process

. The liquid cluster that is extruded at the

pressure performs the mechanical work of the isobaric-isothermal expansion of the

working medium (the reduction of the interface area) according to the equation (2):

The final Stroke IV ends with the return of nanopore 1 and cluster 2 to the initial

state (start of Stroke I in Fig. 7)

As a result of the four-stroke cycle inside the system, the mechanical work

was done by the accumulated heat :

4-223

. (7)

An approximative degree of the real thermal efficiency to the thermal efficiency

of Carnot cycle is defined as:

where is the admitted heat in the cycle, is the thermal

efficiency of the ideal Carnot cycle, is the total heat

capacity of the system ( and are the specific heat capacities of the liquid and the

pore material respectively, and are the liquid and pore material densities).

In the case where , which can be implemented by selecting

the physical characteristics of the liquid and of the matrix , and

considering the matrix with the pores of molecular size (e.g., zeolites [52,

53, 59, 61]) the thermal efficiency of the considered cycle can approach the thermal

efficiency of the ideal Carnot cycle but never reach it since in fact the

conditions or , and are unattainable.

The thermodynamic compactness (TC) for the new thermodynamic cycle is

determined by the formula:

For the proposed cycle the TC is 100 times higher than the TC of traditional

cycles (all the present-thermal machines and machineries have the same order of

magnitude of the TC that is about 200–550 J/m3K) [73].

3.5 Other applications of heterogeneous lyophobic systems

Taking into account the large number of unusual properties of new working

media, the range of its applications can be quite broad. Thus, by studying HLS based

on electrolytes and different matrices [32, 31, 56,42,43, 75, 45], Qiao et al. developed

so-called volume memory liquid [56], which have a much higher specific energy

density (0.70 J / g) compared to, for example, the alloys of Ti-Ni (0.05 J / g).

HLS with significant hysteresis may be used to create compact antiseismic

systems [6, 7], with weight and dimensional advantages similar to those of HLS-based

shock-absorbers. Another important advantage of such systems should be mentioned:

efficient energy dissipation of earth tremors occurs even at low frequency of their

exposure, while the traditional hydraulic systems, by their physical nature, can not

dissipate the energy of the low-frequency effects (in accordance with Newton's law,

the flow resistance of viscous fluid is proportional to the velocity. Hence, low speed

(frequency) causes low dissipation of energy).

Conclusions

Since Faraday scientists and engineers knew that colloidal systems have huge

interfacial areas which contain immense reserves of the surface energy, unfortunately

4-224

bound energy. The usage of repulsive effect caused by intermolecular interactions on

this surface made it possible to release surface energy and utilize it for useful work.

Thermomolecular energetics (TME) is a new direction in technical

thermodynamics. Its object is new working media – interface in “non-wetting liquid +

porous solid” condensed heterogeneous lyophobic system (HLS). HLS has the

properties of molecular spring. For the first time the problem of energy storage and

conversion in the thermo-mechanical systems is not handled by means of kinetic

energy of gas and vapor molecules, as it is successfully done since the first industrial

revolution, but by making use of the potential energy of intermolecular interactions on

the huge interfacial surfaces of the HLS.

The application of HLS in the field of thermal and nuclear power and in power

engineering allows to develop compact and high-performance devices for energy

storage, conversion and dissipation (see paragraph 3), and as a result, significantly

reduce the consumption of construction materials and fuel and to improve the

environmental performance of equipment (often water is used as liquid for HLS).

A wide range of fundamental and applied studies on TME conducted in various

countries (France [16–24, 29–31, 33, 35, 38, 52, 53, 55, 57–61,] USA [32, 34, 42,43,

45, 46, 50, 56, 66, 75], Japan [65, 69–72, 85, 86], Ukraine [8, 9, 23, 25, 28, 37, 39, 67,

68, 84], Russia [26, 36, 40, 41, 48, 49, 54, 74], Spain [47– 49], South Korea [62,63],

etc.) created the conditions for the organization of international cooperation in the

field of TME under the joint coordinated program. Such cooperation would lead to a

better integration of segmentary (separated) scientific and technological results in

different scientific centers (after all, TME is multidisciplinary direction). And would

promote rapid industrialization of TME concepts based on use of the new two-

dimensional working media - "liquid-solid" interface on which the intermolecular

forces cause an effect of repulsion.

References

[1] V. A. Eroshenko. Hydro-capillary accumulator. USSR (1980) – Russian (1993)

Patent 943,444.

[2] T. Reis. Introduction a la Chimie–Physique des Surfaces. Paris: Dunod. (1952).

P.286.

[3] L. D. Landau, E. M. Lifshitz. Statistical Physics. 3d Edition. Butterworth-

Heinemann. (1980). P.544.

[4] A. W. Adamson, A. P. Gast. Physical Chemistry of Surfaces. 6th

Edition. Wiley.

(1997). P. 784.

[5] V. A. Eroshenko. Thermodynamics of penetration of liquid metals into rigid

porous matrices. Capillary properties and adhesion of alloys. Kyiv: Naukova dumka.

(1987). P. 100–109.

[6] V. A. Eroshenko. Russian-Soviet Patents No. 943,444 (1980); 1,382,078 (1982);

1,380,357 (1983); 1,333,870 (1985); 1,434,881 (1985); 1,452,262 (1986); 1,508,665

(1987).

[7] V. A. Eroshenko. Proceedings of Int. Post–SMITR Conf. Seismic Isolation,

passive Energy Dissipation and active Control of Seismic Vibrations of Structure.

Taormina. Sicily. Italy. (1997). p. 783.

[8] V. A. Eroshenko and Yu F. Lazarev. Rheology and dynamics of repulsive

clathrates. J. of Applied Mechanics and Technical Physics. 53(1). (2012). 98-112.

[9] V. A. Eroshenko and Ya G. Grosu. Maxwell’s relations and thermal coefficients

for repulsive clathrates. J. of Technical Physics. 58(8). (2013). 1087-1093.

4-225

[10] G. V. Lisichkin, A. A. Serdan, S. M. Staroverov, A. Y. Yaffa. Modified silica

sorption, catalysis and chromatography (in Russian). М.: Chemistry. (1986). P.247.

[11] V. A. Eroshenko and A. Y. Fadeev. Intrusion and Extrusion of Water in

Hydrophobized Porous Silica. Colloid J. 57(4). (1995). 446 – 449.

[12] A. Y. Fadeev, V.A. Eroshenko. Hydrophobic and Superhydrophobic Chemically

Modified Porous Silicas: Investigation of Wetting with Water (in Russian).

Mendeleev Chemistry J. 39(6). (1995). 93–103.

[13] V. A. Eroshenko, A.Y. Fadeev. Water porosimetry for hydrophobic porous

materials investigation (in Russian). Mendeleev Chemistry J. 40(1). (1996). 92-99.

[14] A. Y. Fadeev and V. A. Eroshenko. Study of Penetration of Water into

Hydrophobized Porous Silica. J. Colloid Interface Sci. 187(2). (1997). 275-282.

[15] G. V. Lisichkin, A. Y. Fadeev, A. A. Serdan, P. N. Nesterenko, P.G. Mingalev,

D. B. Furman. Chemistry of Grafted Surface Compounds. М.: Fizmatlit. (2003). P.

592.

[16] M. Trzpit, M. Soulard, J. Patarin. Water intrusion-extrusion in silicalite-1 with

tunable mesoporosity prepared in fluoride medium. J Mater Sci. 44(24). (2009).

6525–6530.

[17] L. Tzanis, M. Trzpit, M. Soulard, J. Patarin. High pressure water intrusion

investigation of pure silica 1D channel AFI, MTW and TON-type zeolites.

Microporous and Mesoporous Materials. 146 (1). (2011). 119–126.

[18] M. A. Saada, M. Soulard, B. Marler, H. Gies and J. Patarin. High-Pressure Water

Intrusion Investigation of Pure Silica RUB-41 and S-SOD Zeolite Materials. J. Phys.

Chem. C. 115(2). (2011). 425–430.

[19] L. Tzanis, M. Trzpit, M. Soulard and J. Patarin. Energetic Performances of STT-

Type Zeosil: Influence of the Nature of the Mineralizing Agent Used for the

Synthesis. J. Phys. Chem. C. 116(7). (2012). 4802-4808.

[20] L. Tzanis, B. Marler, H. Gies and J. Patarin. High-Pressure Water Intrusion

Investigation of Pure Silica ITQ‑7 Zeolite. J. Phys. Chem. C. 117(8). (2013).

4098−4103

[21] N. Gokulakrishnan, T. Karbowiak, J. P. Bellat, L. Vonna, M.-A. Saada, J. L.

Paillaud, M. Soulard, J. Patarin, J. Parmentier. Improved hydrophobicity of inorganic–

organic hybrid mesoporous silica with cage-like pores. Colloids and Surfaces A:

Physicochem. Eng. Aspects. 421. (2013). 34– 43.

[22] M. Trzpit, M. Soulard, J. Patarin, N. Desbiens, F. Cailliez, A. Boutin, I.

Demachy, and A. H. Fuchs. The Effect of Local Defects on Water Adsorption in

Silicalite-1 Zeolite: A Joint Experimental and Molecular Simulation Study. Langmuir.

23(20). 2007. 10131-10139.

[23] T. Karbowiak, M.-A. Saada, S. Rigolet, A. Ballandras, G. Weber, I. Bezverkhyy,

M. Soulard, J. Patarin, J.-P. Bellat. New insights in the formation of silanol defects in

silicalite-1 by water intrusion under high pressure. Phys. Chem. Chem. Phys. 12(37).

(2010). 11454–11466.

[24] O.V. Ievtushenko, V.A. Eroshenko, Ya.G. Grosu, J.-M. Nedelec, J.-P.E. Grolier.

Evolution of the energetic characteristic of {silicalite-1 + water} repulsive clathrates

in a wide temperature range. Phys. Chem. Chem. Phys. 15(12). (2013). 4451–4457.

[25] V. A. Eroshenko. Non-ordinary properties of a complex thermodynamic system.

C. R. Acad. Sci. Ukraine, Ser. A. 10. (1990). 79.

[26] V. Yu. Gusev. On Thermodynamics of Permanent Hysteresis in Capillary

Lyophobic Systems and Interface Characterization. Langmuir. 10(1). 1994. 235-240.

[27] V. A. Eroshenko. Non-Compressibilite et Non-Dilatabilite Adiabatiques d’un

Systeme Thermodynamique Complexe. Entropie. 32(196). (1996). 17–23.

4-226

[28] V.A. Eroshenkoa, V.P. Stoudenets. The influence of developed interfaces upon

the heterogeneous nanosystem thermal capacity. Composites: Part A. 33(10). (2002).

1349–1353.

[29] B. Lefevre, A. Saugey, J.L. Barrat, L. Boquet, E. Charlaix, P.F. Gobin, G. Vigier.

Intrusion and extrusion of water in hydrophobic mesopores. J. Chem. Phys. 120.

(2004). 4927–4938.

[30] B. Lefevre, A. Saugey, J.L. Barrat, L. Boquet, E. Charlaix, P.F. Gobin, G. Vigier

Intrusion and extrusion of water in highly hydrophobic mesoporous materials: effect

of the pore texture. Coll. Surf. A. 241. (2004). 265–272.

[31] L. Coiffard, V.A. Eroshenko, J.-P.E. Grolier. Thermomechanics of the Variation

of Interfaces in Heterogeneous Lyophobic Systems. AIChE J. 51(4). (2005). 1246–

1257.

[32] Y. Qiao, V.K. Punyamurtula, A. Han, X. Kong, F.B. Surani. Temperature

dependence of working pressure of a nanoporous liquid spring. Appl. Phys. Lett.

89(25). (2006). 251905.

[33] L. Coiffard, V.A. Eroshenko. Temperature effect on water intrusion/expulsion on

grafted silica gels. J. of Colloid and Interface Sci. 300(1). (2006). 304–309.

[34] A. Han, Y. Qiao. Pressure-Induced Infiltration of Aqueous Solutions of Multiple

Promoters in a Nanoporous Silica. J. Am. Chem. Soc. 128(32). (2006). 10348–10349.

[35] L. Guillemot. Ph.D. Thesis. Institut National des Sciences Appliquees de Lyon.

(2010).

[36] V.D. Borman, A.A. Belogorlov, V.A. Byrkin, G.V. Lisichkin, V.N. Tronin and

V.I. Troyan. The infiltration of nonwetting liquid into nanoporous media and the

thermal effect. Journal of Physics: Conference Series. 291(1). (2011). 012044.

[37] O.V. Ievtushenko, V.P. Stoudenets, V.A. Eroshenko. Effective thermal

conductivity of the heterogeneous lyophobic nanosystems for the usage in

thermomechanical energy devices. International Journal of Thermal Sciences. 62.

(2012). 103–108.

[38] L. Guillemot, T. Biben, A. Galarneau, G. Vigier, E. Charlaix. Activated drying in

hydrophobic nanopores and the line tension of water. Proc. Natl. Acad. Sci. USA.

109(48). (2012). 19557–62.

[39] V. A. Eroshenko, Y.G. Grosu. Thermodynamic and Operational Properties of

Heterogeneous Lyophobic Systems. International Journal of Thermodynamics. 16(1).

(2013). 1-9.

[40] V. D. Borman, A. A. Belogorlov, A. M. Grekhov, G. V. Lisichkin, V. N. Tronin,

V. I. Troyan. The percolation transition in filling a nanoporous body by a nonwetting

liquid. Journal of Experimental and Theoretical Physics. 100(2). (2005). 385-397.

[41] V. D. Borman, A. A. Belogorlov, G. V. Lisichkin, V. N. Tronin, V. I. Troyan

Investigation of the dynamics of a percolation transition under rapid compression of a

nanoporous body-nonwetting liquid system. Journal of Experimental and Theoretical

Physics. 108(3). (2009). 389-410.

[42] A. Han, Y. Qiao. Infiltration pressure of a nanoporous liquid spring modified by

an electrolyte. J. Mater. Res. 22(3). 2007. 644–648.

[43] A. Han, X. Chen, Y. Qiao. Effects of the Addition of Electrolyte on Liquid

Infiltration in a Hydrophobic Nanoporous Silica Gel. Langmuir. 24(14). (2008).

7044–7047.

[44] J. Zhao, P.J. Culligan, J. T. Germaine, X. Chen. Experimental Study on Energy

Dissipation of Electrolytes in Nanopores. Langmuir. 25(21). (2009). 12687–12696.

4-227

[45] L. Liu, H. Lim, W. Lu, Y. Qiao, X. Chen. Mechanical-to-electrical energy

conversation by mechanically driven flow of electrolytes confined in nanochannels.

Appl. Phys. Express 6. (2013). 015202.

[46] L. Liu, J. Zhao, P. J. Culligan, Y. Qiao and X. Chen. Thermally Responsive Fluid

Behaviors in Hydrophobic Nanopores. Langmuir. 25(19). (2009). 11862–11868.

[47] Y. G. Bushuev and G. Sastre. Feasibility of Pure Silica Zeolites J. Phys. Chem.

C. 114 (45). (2010). 19157-19168.

[48] Y. G. Bushuev and G. Sastre. Atomistic Simulation of Water Intrusion/Extrusion

in ITQ-4 (IFR) and ZSM-22 (TON): The Role of Silanol Defects. J. Phys. Chem. C.

115(44). 2011. 21942–21953.

[49] Y. G. Bushuev, G. Sastre, J.V. J.-O. and J. G lve . ater− ydrophobic eolite

Systems. J. Phys. Chem. C. 116(47). (2012). 24916−24929.

[50] B. Xu, B. Wang, T. Park, Y. Qiao, Q. Zhou and X. Chen. Temperature

dependence of fluid transport in nanopores. J. Chem. Phys. 136(18). (2012). 184701.

[51] V.A. Eroshenko. Heterogeneous structure for accumulation or dissipation of

energy, process to use it and associated devices. Int. Patent WO 96/18040 (1996).

[52] V. A. Eroshenko, R.-C. Regis, M. Soulard and J. Patarin. Energetics: A New

Field of Applications for Hydrophobic Zeolites. J. Am. Chem. Soc. 123(33). (2001).

8129-8130.

[53] V. A. Eroshenko, R.-C. Regis, M. Soulard and J. Patarin. The heterogeneous

systems ‘water–hydrophobic eolites’: new molecular springs. C.R.P YSIQUE. 3(1).

2002. 111–119.

[54] V.D. Borman, A.A. Belogorlov, A.M. Greckhov, G.V. Lisichkin, V.N. Tronin

and V.I. Troyan. The mechanism of Mechanical Energy Accumulation in Nonwetting

Liquid – Nanoporous Solid System. Techn. Phys. Lett. 30(12). (2004). 973–975.

[55] M. Trzpit, M. Soulard and J. Patarin. The Pure Silica Chabazite: A High Volume

Molecular Spring at Low Pressure for Energy Storage. Chem. Lett. 36(8). (2007).

980–981.

[56] A. Han, Y. Qiao. A volume-memory liquid. Appl. Phys. Lett. 91(17). (2007).

173123.

[57] M. Trzpit, M. Soulard, J. Patarin. Water intrusion in mesoporous silicalite-1: An

increase of the stored energy. Microporous and Mesoporous Materials. 117(3).

(2009). 627–634.

[58] L. Guillemot, A. Galarneau, G. Vigier, T. Abensur, E. Charlaix. New device to

measure dynamic intrusion/extrusion cycles of lyophobic heterogeneous systems. Sci.

Instrum. 83(10). (2012). 105105.

[59] L. Tzanis, M. Trzpit, M. Soulard and J. Patarin. Energetic Performances of

Channel and Cage-Type Zeosils. J. Phys. Chem. C. 166(38). (2012). 20389–20395.

[60] G. Ortiz, H. Nouali, C. Marichal, G. Chaplais and J. Patarin. Energetic

performances of the metal-organic framework ZIF-8 obtained using high pressure

water intrusion-extrusion experiments. Phys. Chem. Chem. Phys. 15(14). (2013).

4888-4891.

[61] N. Gokulakrishnan, J. Parmentier, M. Trzpit, L. Vonna, J. L. Paillaud and M.

Soulard. Intrusion/Extrusion of Water Into Organic Grafted SBA-15 Silica Materials

for Energy Storage. Journal of Nanoscience and Nanotechnology. 13(4). (2013).

2847–2852.

[62] B. Y. Moon, B. S. Kang, J. Kim, W. J. Song. Experimental study on mechanical

damping system using colloid suspension. Key Engineering Materials. 274. (2004).

775-780.

4-228

[63] T.W. Ku, S.B. Jeon, V.H. Bui, W.J. Song. Numerical and experimental approach

on energy dissipation in nano colloidal damper Journal of Mechanical Science and

Technology. 21(10). (2007). 1464–1470.

[64] V.A. Eroshenko. Damper with high dissipating power. Int. Pat. WO 01/55616

A1. (2001).

[65] C.V. Suciu, T. Iwatsubo, S. Deki. Investigation of a colloidal damper. J. Colloid

and Interface Sci. 259(1). (2003). 62–80.

[66] F.B. Surani, X. Kong, D.B. Panchal and Y. Qiao, Appl. Energy absorption of a

nanoporous system subjected to dynamic loadings. Phys. Lett. 87(16). (2005).

163111.

[67] V.A. Eroshenko. A New Paradigm of Mechanical Energy Dissipation. Part 1:

Theoretical Aspects and practical Solutions. Journal Proceedings of Mechanical

Engineers, Part D: Journal of Automobile Engineering. 221(3). (2007). 285–300.

[68] Eroshenko VA, Piatiletov II, Coiffard L, and Stoudenets VP. A New Paradigm of

mechanical Energy Dissipation. Part 2: Experimental Investigation and effectiveness

of a novel Damper. Journal Proceedings of Mechanical Engineers, Part D: Journal of

Automobile Engineering. 221(3). (2007). 301–312.

[69] C.V. Suciu, K. Yaguchi. Endurance Tests on a Colloidal Damper Destined to

Vehicle Suspension. Experimental Mechanics. 49(3). (2009). 383–393.

[70] C.V. Suciu, S. Tani, K. Miyoshi. Experimental study on thermal Characteristics

of a Colloidal Damper. Journal of System Design and Dynamics. 4(6). (2010). 899–

913.

[71] C.V. Suciu, H. Goto. Interconnection between the contact angle (adhesion)

hysteresis, slippage on a nanorough solid wall and phononic friction. Tribology

International. 43(5). (2010). 1091–1098.

[72] C. V. Suciu. Ride-comfort of an automobile equipped with colloidal dampers at

its frontal suspension. Proc. Int. Conf. on Noise and Vibration Eng. (2010).

[73] V.A. Eroshenko. Heterogeneous Thermodynamic System. Eroshenko Cycle of

Transformation of Thermal Energy into Mechanical Energy and Devices to Achieve It

(in Russian). Soviet-Russian Patent No. 1,254,811 (1981).

[74] V.S. Egorov, A.G. Portyanoy, A.P. Sorokin, V.G. Maltsev, R.M. Voznesensky,

A.P. Ivchenko. Thermally sensitive starting device. Russian patent №2138086 (1996).

[75] W. Lu, T. Kim, A. Han, X. Chen, Y. Qiao. Eletrowetting Effect in a Nanoporous

Silica. Langmuir. 25(16). (2009). 9463–9466.

[76] V. A. Eroshenko. Thermomolecular energetics. Industrial Heat Engineering. 14

(1–3). (1992). 22 – 25.

[77] V. A. Eroshenko. Heterogeneous structure for accumulating or dissipating

energy, methods of using such a structure and associated devices. U.S. Patent No

6,052,992. (2000).

[78] E. W. Washburn. The dynamics of capillary flow. Phys. Rev. 17(3). (1921). 273–

283.

[79] V.A. Eroshenko. Dimensionality of space as a thermodynamic potential of the

system (in Russian). Proceedings of the Ukraine Acad. Sci. 5. (1993). 65–67.

[80] V. A. Eroshenko. Heat transfer during filling of phobic capillaries. Colloid J. 5.

(1987). 875–880.

[81] V. A. Eroshenko. Influence of the specific interfacial area in a heterogeneous

lyophobic system on thermal effects observed in the process of its isothermal

compression. Mendeleev Chemistry J. 46(3). 2002.

4-229

[82] I. Egry, E. Ricci, R. Novakovic, S. Ozawa. Surface tension of liquid metals and

alloys—Recent developments. Advances in colloid and interface science. 159(2).

(2010). 198-212.

[83] U. Domańska, M. Królikowska. Effect of temperature and composition on the

surface tension and thermodynamic properties of binary mixtures of 1-butyl-3-

methylimidazolium thiocyanate with alcohols. J. Colloid Interface Sci. 348(2). (2010).

661-667.

[84] V.A. Eroshenko, T.L. Yarosh. Synthesis of Fluid with a Large Value of the

Temperature Coefficient of Surface Tension–Imperative in the Era of Universal

Energy. Research Bulletin of NTUU "KPI". 2. 2012. 37.

[85] C.V. Suciu, T. Iwatsubo, K. Yaguchi, M. Ikenaga. Novel and global approach of

the complex and interconnected phenomena related to the contact line movement past

a solid surface from hydrophobized silica gel. J. Colloid Interface Sci. 283(1). (2005).

196–214.

[86] T. Iwatsubo, C.V. Suciu, M. Ikenagao, K. Yaguchio. Dynamic characteristics of

a new damping element based on surface extension principle in nanopore. Journal of

Sound and Vibration. 308(3). (2007). 579–590.