Reversible Wetting in Nanopores for Thermal Expansivity Control

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Reversible Wetting in Nanopores for Thermal Expansivity Control: From Extreme Dilatation to Unprecedented Negative Thermal Expansion Yaroslav Grosu, Abdessamad Faik, Jean-Marie Nedelec, and Jean-Pierre E. Grolier J. Phys. Chem. C, Just Accepted Manuscript • Publication Date (Web): 05 May 2017 Downloaded from http://pubs.acs.org on May 6, 2017

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The Journal of Physical Chemistry C is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

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The Journal of Physical Chemistry

Figure 1. Isobaric coefficient of thermal expansion of NHLS calculated using equations (5a) and (5b) having respectively a) narrow pore size distribution and b) broad pore size distribution. 288x174mm (150 x 150 DPI)

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Figure 1. Isobaric coefficient of thermal expansion of NHLS calculated using equations (5a) and (5b) having respectively a) narrow pore size distribution and b) broad pore size distribution. 270x162mm (150 x 150 DPI)


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Figure 2. PV-isotherms of a) {HC18 + water} NHLS at 275K; b) {HC18 + water} NHLS at 325K; c) {ZIF-8 + water} NHLS at 275K and d) {ZIF-8 + water} NHLS at 325K. 288x201mm (300 x 300 DPI)



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Figure 3. Relative volume change of a) {HC18 + water} NHLS at atmospheric pressure upon heating and b) {ZIF-8 + water} NHLS at constant pressure of 23.8 MPa upon cooling 288x201mm (300 x 300 DPI)



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Figure 3. Relative volume change of a) {HC18 + water} NHLS at atmospheric pressure upon heating and b) {ZIF-8 + water} NHLS at constant pressure of 23.8 MPa upon cooling 288x201mm (300 x 300 DPI)


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Figure 4. Isobaric thermal expansion coefficient of a) {HC18 + water} NHLS at atmospheric pressure upon heating and b) {ZIF-8 + water} NHLS at constant pressure of 23.8 MPa upon cooling 288x201mm (300 x 300 DPI)



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Figure 4. Isobaric thermal expansion coefficient of a) {HC18 + water} NHLS at atmospheric pressure upon heating and b) {ZIF-8 + water} NHLS at constant pressure of 23.8 MPa upon cooling 288x201mm (300 x 300 DPI)


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Figure 5. Adjustment of the parameters of equations (3) using experimental compressibility of {HC18 + water} NHLS. 286x192mm (150 x 150 DPI)



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TOC Graphic 44x27mm (300 x 300 DPI)


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Reversible Wetting in Nanopores for Thermal Expansivity Control: from Extreme Dilatation to Unprecedented Negative Thermal Expansion 1,2,3,* Yaroslav Grosu , Abdessamad Faik 3, Jean-Marie Nedelec 1, Jean-Pierre Grolier 1 1

, CNRS, SIGMA Clermont, ICCF, F-63000, Clermont-Ferrand,

France 2 Laboratory of Thermomolecular Energetics, National Technical University of Ukraine “Ky P y ch c I ”, P . P y 37, 9 03056 Ky , k a 3 CIC Energigune, Albert Einstein 48, M a a a) 01510, Spain, [email protected] Abstract. In this work a general thermodynamic grounds as well as their experimental verification are given to demonstrate how a reversible wetting process of a liquid in nanopores provoked by a temperature variation can be used to develop systems with the necessary thermal expansion behavior. Thermal expansion coefficients of such nanoporous heterogeneous lyophobic systems can be controlled in the unprecedentedly wide range of both negative and positive values. Perspectives as well as challenges on the way of the full potential use of proposed mechanism are identified. 1. Introduction Thermal expansion is a basic characteristic of a material or a system considered important not only in nearly every field of science and technology, but also in other aspects of our life. It is very common in nature that a body expands/shrinks upon heating/cooling exhibiting positive thermal expansion (PTE) 1. Such behaviour can be useful as it represents the process of thermal to mechanical energy transformation, but also can be undesirable when invariable dimensions within some temperature range are required. In the former case the rare phenomenon of negative thermal expansion (NTE) shrinking/expanding upon heating/cooling 1-4 - becomes very useful to compensate for PTE and to reach zero thermal expansion, which is critical for applications like high precision optics, electronics, photonics, mechanics etc. 4-6 In any of these cases, PTE or NTE, it is obviously important to be able to control the thermal expansion in terms of both its magnitude and temperature range. In recent years the topic of NTE generated an increasing interest for scientific and industrial communities 3, 7-24. Numerous works are dedicated to the development of materials with pronounced NTE and its control in a required temperature range. Particularly, in very recent works Engel et al. investigated organic systems demonstrating NTE 7. Feasibility of using multi-walled carbon nanotubes for the control of coefficients of 1 ACS Paragon Plus Environment


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thermal expansion of composite materials was evaluated in the work of Shirasu et al. 8. Wang et al. fabricated a range of mechanical metamaterials with adjustable NTE 9. Ca3– xSrxMn2O7 perovskite was investigated in terms of NTE control by adjusting the composition 10. Colossal negative thermal expansion in reduced layered ruthenate was finally reported by Takenaka et al. 11 In general the most known materials with NTE are the cubic zirconium tungstate family ZrW2O8 3, some zeolites and zeolite-like materials 12, the family of AM2O7 compounds (where A = U, Th, Zr, Hf, Sn and M = P and V), 13 Cd(CN)2, ReO3, 14,15 and NaZn13-type La(Fe, Si, Co)13 compounds 16. For most of known materials which demonstrate NTE, the value of isobaric thermal coefficient is ca. . However, for some materials, higher values were reported: for ScF3 and for Ca0.8La0.2Fe2As2 18. The apparent NTE value of was reported for nanoporous fluorous metal organic framework (FMOF1) due to sorption of N2 molecules during the cooling process 19. Takenaka reported for reduced layered ruthenate 11. 17

There are also some works on the , along the

a

c

ffic

f

orientation. Particularly,

a

h

a

xpa was

reported for NaZn13-type La(Fe, Si, Co)13 compounds 16 and for porous polyacrylamide 20 polymer film with . Some of the highest values of c-axial linear negative thermal expansion were also reported for pentamorphic organometallic 21 martensite reaching values of , for Ag3[Co(CN)6] with 22, 23 , for FMOF-1 with under vacuum, 19 for (S,S)octa-3,5-diyn-2,7-diol with maximum value of , 24 but due to exceptionally large values of positive thermal expansion along the and axes, overall (volumetric) thermal expansion of indicated materials is positive and is very large. There are certainly less works on PTE, as this effect is classical and is well known. Fabini et al. investigated positive thermal expansion in hybrid formamidinium lead iodide pervoskite.25 MZrF6 series (M = Ca, Mn, Fe, Co, Ni and Zn) were explored in terms of thermal expansion control from positive to negative.26 The use of positive thermal expansion as an actuator still remains an explored topic. 27 Tailoring the expansion of metal alloys was demonstrated in reference 28. Previously we demonstrated that a system consisting of a porous material and a non-wetting liquid (nanoporous heterogeneous lyophobic system (NHLS)) can exhibit both exceptional negative thermal expansion 29,30 and extreme dilatation behaviours 31 with orders of magnitude higher absolute values of thermal coefficient compared to other 2 ACS Paragon Plus Environment

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materials and controlled temperature range. Such high values are reached due to reversible intrusion-extrusion process of non-wetting liquid into porous material induced by temperature variation: since the liquid is non-wetting with respect to the porous solid, it does not penetrate inside the pores under ambient conditions, however, temperature variations can provoke intrusion or extrusion of a non-wetting liquid (depending on the NHLS) leading to pronounced volume variation. Due to such unconventional mechanism NHLS (which is typically in the form of a suspension) demonstrates orders of magnitude higher volume variation upon temperature change in comparison with solids. It is of high importance that both positive and negative thermal expansions of an NHLS can be easily controlled in terms of magnitude and temperature range by the pore size distribution of the solid and by the degree of non-wetting condition. In this work we generalize the theoretical basis for the mechanism responsible for different thermal expansion of an NHLS, demonstrating how it can be controlled in terms of magnitude, sign (positive or negative) and temperature range through the basic properties of the porous material and non-wetting liquid. Next we validate obtained conclusions with some experimental data. 2. Experimental section. In this work two NHLSs were used based on microporous metal-organic framework ZIF-8 and mesoporous grafted silica gel HC18. ZIF-8 was purchased from Sigma Aldrich as Basolite Z1200 (Zeolitic imidazolate framework), it consists of cage-like pores of ~1.16 nm diameter connected by 6-ring windows of ~0.34 nm and is characterized by a huge specific surface area of c.a. 1800 m2/g. The porosity of material was determined as 0,38 cm3/g by nitrogen gas sorption. HC18 stands for Hypersil 5u HS C18. It is a mesoporous silica grafted by linear chains of octylsilanes (C18H37) purchased from Hypersil. It has two-peak pore size distribution in the 3-11 nm range (Figure S1), surface of 140 m2/g and pore volume of 0.4 cm3/g. Water was used as non-wetting liquid for these hydrophobic porous materials. d fi d ST-7M transitiometer of the ST-7 model instrument (BGR-Tech) was used under isothermal conditions, with the simultaneous recording of pressure and volume and also under isobaric conditions, with simultaneous recording of temperature and volume. Detailed description of experimental setup is given elsewhere. 67 A stability of the ZIF-8 samples before and after the intrusion-extrusion cycles was verified by XRD analysis using a Bruker D8 Advance X-ray diffractometer equipped with a LYNXEYE detector using CuKα1 radiation (λ= 1.5418 Å) and θ-2θ geometry. The data were collected at room temperature between 3° and 110° in 2θ with a step size of 0.02° and counting time of 8 s per step. 3 ACS Paragon Plus Environment


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3. Results and discussion Thermodynamic description of NHLS. Systems consisting of a porous material and a non-wetting liquid - heterogeneous lyophobic systems - have been considered for energy applications and were investigated extensively in the last years. 32-79 The operational principle based on reversible forced intrusion - spontaneous extrusion of non-wetting liquid into-from the pores was considered promising for mechanical energy storage 34,38,58,63,64 or dissipation 35, 41-57, 79 due to several advantages compared to conventional working bodies, like system charge (intrusion) - discharge (extrusion) at constant pressure, 33,34,38 absence of overheating upon operation even at high frequencies, 35,39,40,79 high energy density. 37-39 In what follows we make an attempt to develop a general thermodynamic description of NHLS, with a particular focus on the isobaric conditions, which are explored very poorly in the literature at the moment. Equation of state. In our previous works it was demonstrated that thermodynamical description of NHLS requires consideration of not only the bulk effects (determined by the properties of a porous solid and a non-wetting liquid), but also the interfacial effects (determined by liquid intrusion-extrusion process).29,30 Such basis allows writing the equation of state for NHLS in the general form as follows: (1) Where represents connection between pressure (P), temperature (T) and volume variation upon non-wetting liquid intrusion/extrusion into/from porous material ( ); while is the equation of state of the bulk phase of NHLS having volume and consisting of liquid and porous material . While can be defined through known thermal coefficients of liquid and solid, is more complex to express since it must reflect the pore size distribution of a solid, which directly influences the values of pressure and temperature under which intrusion/extrusion takes place. For example, in case the distribution of the pore radius can be described by the Cauchy distribution function 80

with two parameters (average radius an NHLS may be written as:

and its dispersion

), the equation of state for

(2a) or 4 ACS Paragon Plus Environment

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(2b) where is the volume of the pores in the system, is the temperature dependent intrusion/extrusion pressure, is the dispersion of the values of and is normalizing equation at initial pressure temperature

and

.

There is a large number of different distribution functions, which can be used for that matter (Gaussian, LogNormal, Weibull, etc.) 80 and perhaps will be more accurate than the Cauchy function, however we consider Cauchy distribution function as one of the most elegant mathematically wise and easy to work functions for the purposes of demonstrating the proposed NHLS description. Therefore, we use it here for demonstrating purposes, but any other function can be used depending on the best fit to real pore size distribution. The compressibility of the systems can be written using equation (2b) as follows:

It is worth noticing that if the pore size distribution is represented by sets of pores ( being the number of statistical peaks in the pore size distribution, see Figure S1 for the case of ), the equation describing intrusion/extrusion may be expressed by a sum of functions, corresponding to each set of pores:

where

is the function describing the volume variation

or/and temperature provoked intrusion/extrusion into/from the

due to pressure set of pores.

In the equations (2a) and (2b) the parameters and can be defined through the pore size distribution function of a solid. For example, in the simplest case where intrusion/extrusion pressure is defined by the Laplace capillary pressure . Here

is the liquid's surface tension,

the advancing/receding contact angle

and the average pore radius. However, intrusion and extrusion pressures normally require more complex approach to be identified through pore size 42, 55, 79. Particularly for the mesoporous NHLS the bubble nucleation condition for defining extrusion pressure 5 ACS Paragon Plus Environment


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seems to be appropriate. On the other hand, and can be taken directly from experiment of isothermal compression-decompression performed at various temperatures. Now by using definition of isobaric thermal expansion coefficient (2b), one can write for isobaric conditions:

and equation

From equations (5a) it can be seen that the intrusion/extrusion pressure temperature coefficient

defines increase or decrease of the thermal expansion of

the system compared to the thermal expansion corresponding to its bulk components:

In fact in our previous work it was shown experimentally that exceptionally large effect of negative thermal expansion can be reached for NHLSs, 29, 30 as well as pronounced dilatation. 31 Now let us explore how

changes depending on the parameters of equations (5). By

using pertinent literature values of

,

, we explore

the behaviour of the NHLS near intrusion/extrusion conditions on Figure 1 for two different cases of pore size distribution the broadness reflected through intrusion-extrusion dispersion . Figure 1a is for narrow distribution and Figure 1b is for broad distribution .

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Figure 1. Isobaric coefficient of thermal expansion of NHLS calculated using equations (5a) and (5b) having respectively a) narrow pore size distribution and b) broad pore size distribution.

From Figure 1 one can see that depending on the intrusion/extrusion pressure temperature coefficient

thermal expansion of NHLS can change from extreme

dilatation to unprecedented negative thermal expansion with absolute value of . This is orders of magnitude higher compared to known materials with pronounced positive or negative expansion behaviour, with absolute values in the range 7 ACS Paragon Plus Environment


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of . 3, 7-28 While the pore size distribution can be used to control both the value of and the temperature range (in which intrusion/extrusion process contributes to the volume variation). One observes that the broader the pore size distribution, the broader the temperature range, but the lower the maximum absolute value of . In the next section we establish and verify the presented theoretical basis using some experimental results obtained for that purpose. Experimental results and model verification. Mesoporous grafted silica and microporous MOF were chosen to demonstrate that described thermal expansion mechanism does not depend on some specific type of porous material or liquid as long as the non-wetting condition is respected. From Figure 2 it can be seen that both systems demonstrate high level of hydrophobicity (water is strongly non-wetting them), which is evident from rather high intrusion pressures. It can be also observed that each system demonstrates very different behaviour. While for {HC18 + water} NHLS there is no extrusion process at 275K (bumper behaviour) and at 325K extrusion pressure is very low (shock-absorber behaviour) - Figures 2a and 2b; ZIF-8 demonstrates relatively low intrusion-extrusion hysteresis, behaving more like a molecular spring 31, 38, 76 - Figures 2c and 2d. Both systems were verified to be stable after the intrusion-extrusion cycles in this temperature range by means of XRD in case of ZIF-8 (Figure S2) and by means of gas sorption in case of HC18 (Figure S3). Such stability is expected in view of our previous work on ZIF-8 36 and work of Suciu and Yaguchi on the endurance of grafted silica shockabsorbers 35. It is also evident from Figure 2 that both systems demonstrate positive temperature dependence of extrusion pressure

, which according to equation (6b) means

that such systems can be used to demonstrate extreme dilatation of the NHLS. While for intrusion pressure the dependences is positive for {ZIF-8 + water} NHLS negative for {HC18 + water} NHLS

, it is

. As we previously demonstrated how

exceptionally large negative thermal expansion effect can be reached for an NHLS, 29, 30 we focus on the extreme dilatation behaviour in this work, demonstrating that it can be reached by both intrusion and extrusion process following the theoretical basis described above.


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Figure 2. PV-isotherms of a) {HC18 + water} NHLS at 275K; b) {HC18 + water} NHLS at 325K; c) {ZIF8 + water} NHLS at 275K and d) {ZIF-8 + water} NHLS at 325K.

Particularly, for {HC18 + water} NHLS the transformation from bumper to shockabsorber behaviour in the 275-325K temperature range suggests that extrusion of water may be induced by the temperature increase from 275K to 325K under atmospheric pressure. This process is demonstrated in Figure 3. After compression of the {HC18 + water} NHLS at 275K (Figure 2) water remains inside the pores even after pressure is lowered to atmospheric one. Once temperature of the system is increased, extrusion takes place generating huge volume increase (dilatation) of nearly 50% of its initial volume . Experimental thermal expansion coefficient of such system is shown in Figure 4 reaching the maximum value It is orders of magnitude larger compared to known materials with pronounced dilatation. For the {ZIF-8 + water} NHLS due to its high value of extrusion pressure in order to reach the effect of extreme dilatation, experiments were performed under controlled isobaric condition of . Taking advantage of its positive dependence of extrusion pressure (equation 6b) we were able to provoke intrusion of the water into the pores by cooling the system at constant pressure (Figure 3b). The obtained thermal expansion behaviour for this NHLS is similar to the {HC18 + water} NHLS in terms of the 9 ACS Paragon Plus Environment


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magnitude as both systems have similar pore volume and extrusion pressure temperature dependence.

Figure 3. Relative volume change of a) {HC18 + water} NHLS at atmospheric pressure upon heating and b) {ZIF-8 + water} NHLS at constant pressure of 23.8 MPa upon cooling

Figure 4. Isobaric thermal expansion coefficient of a) {HC18 + water} NHLS at atmospheric pressure upon heating and b) {ZIF-8 + water} NHLS at constant pressure of 23.8 MPa upon cooling

The evident difference of isobaric thermal expansion coefficient for the two NHLSs is that {ZIF-8 + water} NHLS demonstrates one peak of (one step intrusion), while {HC18 + water} NHLS demonstrates two peaks of (two steps extrusion). This is due to the differences in pore size distributions of two systems. While ZIF-8 is known to have one statistical peak of pore sizes due to its defined crystalline structure, amorphous silica gel HC18 has two as can be seen from gas sorption analysis (Figure S1), as well as from water intrusion experiment, particularly if one plots compressibility of the system as function of pressure (Figure 5). We now use the {HC18 + water} NHLS to confront the proposed model with experiment, as this system demonstrates more complex behaviour and allows to use an equation of state in its general form (equation (4)) for HLSs based on porous materials with complex pore size distribution (more than one statistical peaks). 10 ACS Paragon Plus Environment

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Figure 5. Adjustment of the parameters of equations (3) using experimental compressibility of {HC18 + water} NHLS.

For that matter first we determine intrusion well as their dispersion

and extrusion

pressures as

. It is easier to do by fitting the theoretical compressibility

(equation (3a)) to compressibility plot (Figure 5). From such fitting one gets , and . Using these parameters in equation (2b) we obtain rather good agreement between theoretical and experimental curves of PV-isotherms (Figure 2b), suggesting that the Cauchy function is a judicious choice for this system. Next by introducing obtained parameters of {HC18 + water} NHLS in equations (5) one may compare the obtained model curve with experiment for volume variation upon temperature change (Figure 3(a)), as well as for isobaric thermal expansion coefficient (Figure 4(a)). Where the temperature coefficient of extrusion pressure was used from experimental data at different temperatures (Figures 2 (a) and (b)). However, in principle such coefficient may be calculated using bubble nucleation approach, which was described in details in previous works 42, 55, 79 and it is out of the scope of this article. From Figure 4 it can be seen that can be predicted by using the proposed approach. Perhaps a more complex distribution function than the Cauchy one can be used to improve the agreement between experiment and model. However, such improvement is purely mathematical and more cumbersome with respect to the thermodynamical approach demonstration, which is the main goal of this work. There could be of course some physical assumptions, which might decrease the predictive aim; like for example the temperature and/or pressure dependence of pore size distribution.



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Retrospective and perspective. At this point it seems that only one application based on pronounced dilatation of NHLS can be found in the early works of Eroshenko. 81 It was shown that previously melted metal alloy intruded inside the pores results in its extrusion upon liquefaction and as a result in pronounced dilatation. Such mechanism was used to create a thermal actuator called "thermal key", 81 which reached an application level as autonomic emergency actuator at a nuclear power plant. 82 The advantage of thermal key is the considerable amount of stored mechanical energy released in a smooth (non explosive) way upon heating it above the metal alloy melting point due to relatively high extrusion pressure. The mechanism of thermal expansion control proposed in this work has a different nature (reversible wetting) and has several advantages compared to "thermal key": 1) ability to work in continuous heating-cooling cycles, while "thermal key" after each discharge (extrusion) must be recharged by means of compression of the NHLS above the intrusion pressure under temperature higher than the melting point of the metal alloy; 2) ability to reach an effect of negative thermal expansion, while thermal key can exhibit only dilatation; 3) intrusion-extrusion cycle in proposed mechanism is not destructive for a porous material, while in "thermal key" crystallization-melting of an alloy inside the pores may have negative (destructive) effect on the structure of a porous material due to a pronounced volume variation inside the nanoconfinement. From the results presented in this and previous works 29 - 31 it clearly appears that NHLSs have unprecedented thermal expansion behaviour compared to known systems in terms of the control of both magnitude and temperature range. However, in order to be able to use the full potential of proposed mechanism there are two highly desirable properties, which must be reached: 1) Negligible intrusion-extrusion hysteresis. The presence of pressure hysteresis in the isothermal compression-decompression cycle (Figure 2) is resulting in a temperature hysteresis in the isobaric heating-cooling cycle, which is certainly non-desirable phenomenon. Particularly, this does not allow us to obtain heating-cooling cycle at the same pressure for studied NHLSs, as such hysteresis leads to very large intrusion and extrusion temperatures difference increasing the necessary temperature range for the cycle beyond the characteristics of our equipment and/or beyond the temperature range where water is in liquid state. We recently reported a new NHLS based on Cu2(tebpz) MOF, which exhibits negligible hysteresis (molecular spring). 76 We further focus our work on reaching the reversible heating-cooling cycle for such NHLSs. 2) Acceptable intrusion/extrusion pressure. It seems that in most cases taking advantage of prominent thermal expansion of NHLSs is more preferable at atmospheric pressure. However, among the great variety of reported NHLSs there is a clear evidence of 12 ACS Paragon Plus Environment

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a deficit of the ones having intrusion-extrusion cycle near atmospheric conditions. This is due to the fact that such systems were considered for mechanical energy storage/dissipation applications, where relatively high operational pressures are required to reach an attractive energy capacity. With this regards deep understanding of the mechanism behind intrusion-extrusion pressure hysteresis is definitely required along with the development of NHLSs with desirable intrusion-extrusion pressures. Conclusions Exceptional variability of thermal expansion behaviour of nanoporous heterogeneous lyophobic systems (NHLSs) was demonstrated theoretically and experimentally. Thermal expansion coefficient of an NHLS not only can reach orders of magnitude higher values compared to best known materials, but its sign (positive or negative) and temperature range can be tuned by the basic characteristics of the NHLS. Such behaviour is due to the unconventional mechanism occurring in a NHLS, i.e. reversible wetting of liquid in nanoporous material induced by temperature variation. Due to the strong orientation of previous works on the use of NHLSs for mechanical energy storage/dissipation applications, the lack of systems with negligible intrusionextrusion pressure hysteresis operating under close to atmospheric pressure is observed. Development of NHLSs with such characteristics would be very beneficial in terms of the potential applications, particularly in the area of negative thermal expansion materials. Supporting Information. Figures of gas sorption isotherms, XRD patterns and pore size distribution. Acknowledgements The help of Cristina Luengo with gas sorption measurements is appreciated. References (1) Evans, J. Negative Thermal Expansion Materials. Dalton Trans. 1999, 19, 3317−3326. 2) Ra a , . V.; N d 147−147.

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