Thesis On Capillary Condensation

X-ray Scattering Study OI Capillary Condensation In Mesoporous Silica
A thesis presented to
the Iaculty oI
the College oI Arts and Sciences oI Ohio University
In partial IulIillment
oI the requirements Ior the degree
Master oI Science
Mayur Sundararajan
May 2013
2013 Mayur Sundararajan. All Rights Reserved.
2
This thesis titled
by
MAYUR SUNDARARAJAN
has been approved Ior
the Department oI Physics and Astronomy
and the College oI Arts and Sciences by
Gang Chen
Assistant ProIessor oI Physics and Astronomy
Robert Erank
Dean, College oI Arts and Sciences
3
ABSTRACT
SUNDARARAJAN, MAYUR., M.S., May 2013, Physics and Astronomy
Director oI Thesis: Gang Chen
The capillary condensation deIorms a nanoporous material due to the capillary
Iorce generated by the Iluid inside the pores. In-situ small and wide angle x-ray
scattering(S/WAXS) were used to study the deIormation with respect to relative vapor
pressure oI the Iluid. Periodic mesoporous silica such as MCM-41 and SBA-15 were
synthesized and used as the samples with water as the capillary condensation agent. The
gas sorption method and SAXS were used to extract the pore parameters oI the samples.
The stresses acting on the silica scaIIold due to the presence oI water in the pores were
deduced by careIul analysis oI various Iorces acting on it. The Poisson`s ratio and elastic
moduli oI the two samples and their annealed Iorms were estimated and compared
quantitatively. Our study demonstrates a novel WAXS-based technique Ior calculating
the mechanical properties oI nanoporous materials with much wider applicability than the
previously reported SAXS technique.
4
DEDICATION
I dedicate this thesis to mv parents M. Sundararafan and S. Jasuki, mv brother S. Arvind,
mv friend K. Maheswari, mv wife S. Poorani and evervbodv who thinks I am
AWESOME''
5
ACKNOWLEDGMENTS
I am grateIul to my advisor Dr. Gang Chen Ior his teaching, guidance and support
Irom the initial to the Iinal stages oI the research. I wish to thank my colleague
Chandrasiri A. Ihalawela Ior all the long discussions and the help with the experiments. I
must thank Dr. Xiaobing Zuo oI Argonne National Laboratory Ior his help to set up the
experiment conducted there. I thank Dr. Alexander Govorov and Dr. David E.J. Tees Ior
serving in my committee.
I take this opportunity to thank all the Iaculty and staII oI the Department oI
Physics and Astronomy Ior aiding in the growth oI both proIessional and personal aspects
oI my liIe in the last couple oI years. I thank all my graduate Iriends Ior the wonderIul
time and especially Chandrasiri, Sneha, Meenakshi, Bijay, Binay Ior supporting and
helping me in various diIIicult situations.
On a personal note, I thank my Iather M. Sundararajan (M.S. EE) Ior treading this
path 27 years ago, which I Iollowed to reach here. I thank my mother S. Vasuki Ior her
encouragement and love. I also thank my Iriend K. Maheswari Ior all the support.
6
TABLE OF CONTENTS
Page
Abstract ............................................................................................................................... 3
Dedication........................................................................................................................... 4
Acknowledgments............................................................................................................... 5
List oI Tables ...................................................................................................................... 8
List oI Eigures ..................................................................................................................... 9
Chapter 1: Introduction..................................................................................................... 13
Chapter 2: Material Synthesis........................................................................................... 17
2.1. MCM41.................................................................................................................. 17
2.1.1. Synthesis mechanism...................................................................................... 17
2.1.2. MCM-41 Synthesis ......................................................................................... 18
2.2. SBA-15 .................................................................................................................. 19
2.2.1. Synthesis mechanism...................................................................................... 19
2.2.2. Synthesis oI SBA-15....................................................................................... 21
Chapter 3: Material characterization................................................................................. 23
3.1. Introduction............................................................................................................ 23
3.2. Gas sorption Method.............................................................................................. 23
3.2.1. Adsorption....................................................................................................... 24
3.2.2. Capillary Condensation................................................................................... 25
3.2.3. Capillary action and the Iormation oI meniscus ............................................. 26
3.2.4. Capillary pressure ........................................................................................... 28
3.2.5. Isotherms......................................................................................................... 29
3.2.6. Kelvin Equation and BJH method .................................................................. 33
3.3. X-ray scattering method......................................................................................... 40
3.3.1. Mechanical parameters ................................................................................... 41
3.3.2. Capillary action oI water as stress .................................................................. 43
3.3.3. X-ray scattering............................................................................................... 49
Chapter 4: Experiment ...................................................................................................... 56
4.1. Gas sorption experiment ........................................................................................ 56
7
4.2. X-ray scattering experiment................................................................................... 57
4.2.1 SAXSess .......................................................................................................... 57
4.2.2. Synchrotron..................................................................................................... 59
4.2.3. Comparison between SAXSess and synchrotron data .................................... 60
Chapter 5: Results and Discussion.................................................................................... 64
5.1. Gas-sorption method:............................................................................................. 64
5.2. X-ray scattering technique: .................................................................................... 65
Chapter 6: Conclusion....................................................................................................... 92
ReIerences......................................................................................................................... 94
Appendix A: Error analysis .............................................................................................. 97
Appendix B: Kelvin Equation........................................................................................... 98
8
LIST OF TABLES
Page
Table 1: Physical pore parameters extracted Irom gas-sorption method.........64
Table 2: Summary oI the stresses acting on the porewall in each plane.......81
Table 3: The poreload modulus estimated by SAXS method...........90
Table 4: The modulus estimated by WAXS...................90
Table 5: Compilation oI the results obtained Irom Gas-sorption, SAXS & WAXS
methods............................91
9
LIST OF FIGURES
Page
Figure 1. Schematic oI the steps in the Iormation oI MCM-41
16
..................................... 18
Figure 2. a) MCM41 aIter calcinations b) The Iinely ground powder and apart oI the
pressed pellet oI MCM-41................................................................................ 19
Figure 3. The presence oI PEO in the walls oI the mesopores in SBA-15
18
. ................... 21
Figure 4. a) The Iiltered part oI the aged solution beIore calcination b) The Iinely ground
powder aIter calcination and a part oI the pellet oI SBA-15. ........................... 22
Figure 5. Adsorption and Capillary condensation. ........................................................... 26
Figure 6. Capillary action and the pressure at diIIerent points......................................... 27
Figure 7. Types oI adsorption isotherms: adsorption (green), desorption (red); iI there is
no change in desorption line Irom adsorption line then it is not represented
separately. ......................................................................................................... 29
Figure 8. Shape oI hysteresis in isotherms and the corresponding pore shapes
27
............ 31
Figure 9. Isotherm oI SBA-15 with nitrogen as adsorptive.............................................. 32
Figure 10. Isotherm oI MCM-41 with nitrogen as adsorptive.......................................... 33
Figure 11. The meniscus with radii r
1
and r
2
inside the pore Iorming the core volume; the
thin layer t oI adsorbate (liquid) on the inner wall ........................................... 35
Figure 12. The table oI BJH method calculation (top) Ior SBA-15, The plot pore volume
vs pore width (bottom) showing the pore size distribution Ior SBA-15. ......... 38
Figure 13. The plot oI pore volume vs pore width showing pore size distribution Ior
MCM-41. .......................................................................................................... 39
Figure 14. Stresses and strains in the three planes. .......................................................... 42
Figure 15. Various levels oI water in the pore with the increase oI RH .......................... 44
10
Figure 16. The Iorces with dashed arrows are on solid due to liquid; Tangential
component(red), Normal component(yellow),Eorce due to Laplace
pressure(maroon);The direction oI surIace tension on each interIace (red solid
arrow);EIIective Iorces on the solid(right). ...................................................... 48
Figure 17. The scattering oI x-rays Irom a planar arrangement oI particles
37
................. 51
Figure 18. Comparison oI SAXS patterns oI MCM-41 at 54 and 86. ....................... 53
Figure 19. Comparison oI WAXS patterns oI MCM-41 at 54 and 86....................... 55
Figure 20. Micromeritics degas system (leIt); Micromeritics Tristar SurIace area and
Porosity(right)
37
................................................................................................ 56
Figure 21. SAXSess instrument and the related devices (leIt); The raw 2D data (right top)
and the converted 1 D data (right bottom). ...................................................... 59
Figure 22. The 1D scattering patterns Irom synchrotron; the arrow indicating the
intensity oI the SAXS peak (top);The arrow indicate the intensity oI the
WAXS peak bottom). ...................................................................................... 62
Figure 23. The 1D scattering pattern Irom the SAXSess indicating the intensity oI the
part oI SAXS peak (top arrow) and the WAXS peak (bottom arrow). ............ 63
Figure 24. Top leIt: SAXS peak position vs RH plot oI MCM-41 AS` ;Top right: SAXS
peak position vs RH plot oI MCM-41 AN`; Bottom leIt: SAXS peak position
vs RH plot oI SBA-15 AS`; Bottom right: SAXS peak position vs RH plot.. 65
Figure 25. The schematic oI the hexagonal arrangement, Irom the Iirst Bragg`s peak in
SAXS the interpore distance is calculated by using the perpendicular triangle.
The area Iilled with red represents the porewall. ............................................. 66
Figure 26. WAXS peak position vs RH plot oI MCM-41 AS`; Top right: WAXS peak
position vs RH plot oI MCM-41 AN`; Bottom leIt: WAXS peak position vs
RH plot oI SBA-15 AS`; Bottom right: WAXS peak position vs RH plot. .... 67
Figure 27. The amplitude oI the Iirst Bragg`s peak oI SAXS vs RH in MCM-41 AS`.
The line represents that the rate oI water loss during capillary evaporation. ... 69
Figure 28. The SAXS intensity and the SAXS strain oI MCM-41 AN` are plotted
together to deduce the data points that are used to calculate the elastic modulus.
.......................................................................................................................... 70
11
Figure 29. The SAXS intensity and the WAXS strain oI MCM-41 AN` are plotted
.......................................................................................................................... 71
Figure 30. The SAXS intensity and the SAXS strain oI SBA-15 AN` are plotted together
to deduce the data points that are used to calculate the elastic modulus. ......... 72
Figure 31. The SAXS intensity and the WAXS strain oI SBA-15 AN` are plotted
.......................................................................................................................... 73
Figure 32. The amplitude oI SAXS Iirst bragg peak vs RH plot Ior SBA-15 AS`. The
lines represent that the rate oI water loss has two diIIerent rates during the
capillary evaporation. ....................................................................................... 74
Figure 33. The strain in the x-y plane extracted Irom the SAXS plotted against ln(RH) Ior
MCM-41AS`. The trendline corresponds to data points(black) beIore the
capillary evaporation. The inset shows the slope and the error in the trendline.
.......................................................................................................................... 76
MCM-41AN`. The trendline corresponds to data points(black) beIore the
.......................................................................................................................... 77
SBA-15AS`. The trendline corresponds to data points(black) beIore the
.......................................................................................................................... 78
SBA-15AN`. The trendline corresponds to data points(black) beIore the
.......................................................................................................................... 79
Eigure 37. The bold blue circles are the stress Iree conIiguration oI pores and the broken
circles represent the change at high RH in x-y plane (SAXS). The pore wall
(right) is drawn Ior cubic arrangement oI pores Ior simplicity. ....................... 82
Figure 38. The bold blue circles are the stress Iree conIiguration oI pores and the broken
circles represent the change at RH beIore capillary condensation. The pore wall
(right) is drawn Ior cubic arrangement oI pores Ior simplicity. ....................... 83
12
Figure 39. The strain calculated Irom ESDP vs the ln(RH) Ior MCM-41 AS`. The
trendline corresponds to the data points(black) beIore the capillary evaporation.
The inset shows the slope and the error in the trendline. ................................. 84
Figure 40. The strain calculated Irom ESDP vs the ln(RH) Ior MCM-41 AN`. The
Figure 41. The strain calculated Irom ESDP vs the ln(RH) Ior SBA-15 AS`. The
Figure 42. The strain calculated Irom ESDP vs the ln(RH) Ior SBA-15 AN`. The
13
CHAPTER 1: INTRODUCTION
In the advent oI nanotechnology, nanomaterials and their properties promise a
wide range oI applications. The physical properties oI bulk materials change as the
material is scaled down to the nanoscale. This change can be attributed to parameters
such as surIace area and surIace tension which were neglected in the bulk state begin to
dominate on the nanoscale. Even the dominant Iorces acting on the material varies: at the
nanoscale, surIace eIIects such as adhesion and cohesion take precedence over gravity
and mass eIIects. A bulk material in its powdered Iorm shows variation in some oI its
physical properties due to the signiIicant increase in the surIace area. II the powder
particles has crevices or pores then the increase in surIace area is large, so the surIace
eIIects deIine its physical characteristics. These materials are broadly known as
nanoporous materials.
These nanoporous materials are classiIied into three categories with respect to
their pore sizes: microporous (2nm), mesoporous (2-50nm) and macroporous (~50nm)
1
.
The microporous materials such as zeolites and active carbons have been studied as early
as mid-twentieth century by Amberg and McIntosh
2
. Some examples oI mesoporous
materials are mesoporous silica and active carbon. Ceramics are a good example oI
macroporous materials. The micro and mesoporous materials have attracted a lot oI
interest due to their wide range oI applications such as catalysts, sorption media and
molecular sieves. The works in mesoporous material and in particular mesoporous silica
began to bloom aIter the discovery oI MCM-41 in the early 1990s
3,4
. MCM is an
acronym Ior Mobil Crystalline Material`. MCM-41 and its variant MCM-48 are
14
mesoporous silica which were synthesized using a template selI assembly mechanism by
researchers at Mobil Oil Corporation. The interesting characteristics oI these materials
are the ability to control the size oI the pores and the ordered arrangement oI pores,
which were missing in zeolites and other microporous materials. This tunability and high
degree oI order, improved it as a molecular sieve and paved the way Ior new applications
such as drug delivery, chemical sensor etc. In the late 1990s, researchers Irom University
oI CaliIornia, Santa Barbara discovered a mesoporous silica material with micropores in
its mesopore wall and this was named as SBA-15
5
. SBA is an acronym Ior Santa
Barbara Amorphous` material. This material also attracted lot oI interest due to its
interconnected pores, which diverges its characteristics Irom MCM-41. In the 2000s,
many researchers began studying the deIormation eIIects in mesoporous silica due to
adsorption and Iound interesting results deviating Irom microporous materials. In this
study, MCM-41 and SBA-15 were synthesized and used as the samples.
The phenomenon oI inducing deIormation on a solid by adsorption has been
studied as early as 1927 by E.T.Meehan
6
. This was Iollowed by similar studies by
Bangham and Eakhoury
7
and they related the deIormation to the decrease in surIace
energy due to adsorption. The later works were more on the deIormation oI micro and
mesoporous materials due to adsorption. Some mesoporous materials such as active
carbons
8
, zeolites
8
and mesoporous silica
9,10
exhibit varying deIormations (i.e. expansion
and contraction). The major diIIerence between adsorption on a typical solid and a
nanoporous solid is the phenomenon oI capillary condensation due to the presence oI
pores. This phenomenon stimulated the interest in researchers to study its eIIects on these
15
materials. The detailed discussion oI this phenomenon will be presented later. Similar
interest drives this study oI physical eIIects on mesoporous silica material due to
capillary condensation.
Capillary condensation in the pores Iills the pore with liquid, which instigates
capillary action
1
. Water rising against gravity in a narrow tube immersed in water is an
example oI capillary action. In nature this allows transportation oI water to the leaves at
the top oI the tree by the roots, blotting up by a towel, transportation oI Iluids in our body
and much more. This capillary action has very interesting eIIects on nanosized
capillaries. When the tubes (capillaries) are on the nanoscale the height the Iluid reaches
and the capillary pressure are humongous. Eor instance, consider a capillary oI width 1
nanometer in water: it exerts a capillary pressure oI 14MPa and the height reached by the
water is 14km. The pressure is comparable to the pressure at the bottom oI the Mariana
trench. In this study, capillary action plays a vital role and it is used as the stress that
deIorms the porous material to measure its strength. A detailed analysis oI capillary
action will be discussed.
The physical parameters such as surIace area, pore volume, pore size distributions
are essential to comprehend and explain the results. There are at least 6 methods to
extract the pore parameters: Gas sorption, Mercury porosimetry, Transmission Electron
Microscopy, Scanning Electron Microscopy, x-ray scattering and neutron scattering
11
. In
this study the gas sorption method was used to extract the pore parameters oI the
mesoporous silica samples. This method is used because oI its simplicity and versatility.
X-ray scattering is used to measure the strain on the silica scaIIold oI the mesoporous
16
silica due to capillary condensation oI water in the porous material. The small angle x-ray
scattering technique has been used Ior the estimation oI that strain
9, 10
but in this study a
novel technique using wide angle x-ray scattering was developed.
The primary aim oI this study is the development oI the new wide angle x-ray
scattering technique to estimate that strain in the mesoporous silica by capillary action oI
water and calculate its Poisson`s ratio and mechanical strength. In the path towards that,
certain ambiguities and missing links in the earlier studies
9, 10
were rectiIied. The samples
oI MCM-41 and SBA-15 used in this study were synthesized in the lab. Each sample was
studied in two diIIerent Iorms, as synthesized (-AS)` and annealed (-AN)`, so the
eIIects oI annealing on the mechanical properties can also be estimated.
The theory and the material synthesis are discussed in the 2
nd
chapter. The theory
oI each method and the important phenomenon used in them are discussed in the 3
rd
chapter. The experiment is detailed in the 4th chapter and its results are presented with
discussion in the 5th chapter.
17
CHAPTER 2: MATERIAL SYNTHESIS
The mesoporous silica materials were synthesized by the template selI-assembly
mechanism. The pore width is controlled by the dimensions oI the template, which
usually is a surIactant or a block polymer. The silica attaches to the template and Iorms
the scaIIold oI the material. The template is removed by calcination leaving the silica
scaIIold. The silica in the scaIIold is amorphous, which is characteristic oI both MCM-41
and SBA-15. The structure oI SBA-15 is more complex than MCM-41 due to the
presence micropores connecting the mesopores. In this section the selI-assembly
mechanism and synthesis oI MCM-41 and SBA-15 are brieIly presented. MCM-41 and
SBA-15 were synthesized in the lab by reIerring to earlier works
19
.
2.1. MCM41
2.1.1. Synthesis mechanism
The synthesis oI MCM-41 can be described in three steps. The main constituents
oI the synthesis are surIactant (Cetyl trimethylammonium bromide (CTAB)) and the
silica precursor (tetra ethyl orthosilicate (TEOS)). In the Iirst step, the surIactants
spontaneously Iorm a rod like arrangement known as a micelle and the micelles become
hexagonally ordered
12,15
. The silicate anions Irom the precursor interact electrostatically
with the surIactant cations and Iorm a layer
12,15
. The diameter oI the enveloping silica
layer is about 50 nm with a number oI micelles encapsulated inside them at the beginning
oI the reaction
13,15
. In the second step, the number oI surIactants decreases resulting in a
smaller pore size (encapsulation)
12,14,15
. The hydrolysis and the condensation oI the
18
silicate precursor take place on the surIace oI the micelle. The second step begins even
beIore the completion oI the Iirst step aIter around three minutes
12
. In the third step, the
silica layer aIter hydrolysis and condensation each encapsulate one micelle and thus the
pore size is approximately 5 nm and become more ordered
12,13,15
. Later the surIactants are
evaporated by calcination at 550C Ior 4hours.
16
.
2.1.2. MCM-41 Synthesis
The synthesis oI MCM-41 is a mixture oI two separately prepared solutions as
Iollows:
Solution 1: 1.6g CTAB 25ml H
2
O 38ml Ethanol 16ml Ammonium Hydroxide
Solution 2: 2.55ml TEOS 5ml Ethanol
Solution1 and Solution2 were stirred separately at 40C Ior 15 minutes beIore mixing and
then the mixed solution was stirred Ior 15 minutes. The solution was aged Ior 48 hrs at
18
12
12,13,15
16
.
Iollows:
2
18
12
12,13,15
16
.
Iollows:
2
19
60C. The aged solution was Iiltered and the sediment was spread into a thin layer on a
ceramic plate. The sediment on the ceramic plate was air dried and was then calcined in
an oven. The calcination process was carried out as Iollows: The sediment was initially
heated to 90C at 1C/min and kept at that temperature Ior 4 hours. It was then heated to
500C at 1C/min and kept at that temperature Ior Iour hours beIore it was naturally
cooled down to 40C. The calcined sample Iorms a dry layer on the ceramic plate. The
layer was scrapped and ground into a Iine powder, some oI which was later pressed into a
13mm diameter pellet to be used in x-ray scattering experiment.
Figure 2. a) MCM41 aIter calcinations b) The Iinely ground powder and a part oI the
pressed pellet oI MCM-41.
2.2. SBA-15
2.2.1. Synthesis mechanism
The block polymer in this synthesis is Pluronic (poly (ethylene glycol)-poly
(propylene glycol)-poly (ethylene glycol) (EO
y
PO
x
EO
y
)) and the silica precursor is
TEOS. The Iormation oI the long-range hexagonally-ordered mesoporous structure is by
a b
20
the selI-assembly template mechanism. The block polymer Iorms micelles at the
beginning oI the synthesis. AIter the hydrolysis oI silicate, it is attracted by van der
Waals Iorce to the micelles. The long range hexagonal order and the attraction oI
hydrolysed silicate attraction happen at the same time
17
. These steps are similar to the
ones discussed Ior MCM-41. Micropores are created by poly ethylene oxide (PEO) in the
surIactant, which interacts with the silicate in the mesopore wall as shown in the Iigure
below. Poly propylene oxide (PPO) is the part oI the polymer which Iorms the template
Ior the mesopores. During calcination along with the rest oI the polymer, the PEO
molecules in the walls evaporate leaving open pores in the mesopore wall
18
.
21
18
2.2.2. Synthesis of SBA-15
The SBA-15 synthesis began with the preparation oI 1.7 M concentrated HCl. 2g
oI P123 (Pluronic P123 (M
av
5800), EO
20
PO
70
EO
20
, (Aldrich)) was added to 11.9g oI
the prepared conc.HCl and 62.9g oI water mixture in a suitable beaker. The beaker was
sealed and the contents were stirred Ior 1 hour at room temperature. Eour grams oI TEOS
solution was added drop by drop into the above solution. The beaker was sealed again
and the contents were stirred Ior 4 hours at 40C. This was Iollowed by aging the solution
Ior 40 hours at 60C. The rest oI the processes (Iiltering, calcinations) were the same as
21
18
av
5800), EO
20
PO
70
EO
20
21
18
av
5800), EO
20
PO
70
EO
20
22
in MCM-41. The sample powder was pressed into pellets Ior the x-ray scattering
experiment.
powder aIter calcination and a part oI the pellet oI SBA-15.
22
experiment.
22
experiment.
23
CHAPTER 3: MATERIAL CHARACTERIZATION
3.1. Introduction
The pore parameters that are necessary Ior this study are surIace area, pore width,
micropore area, pore size distribution oI the sample and strain on the sample due to the
capillary action. A properly synthesized MCM-41 and SBA-15 has hexagonally ordered
porous structure as shown in Eigure 1. The quality oI the synthesized sample was
determined by observing the parameters in the gas sorption method and SAXS. In this
study, the above mentioned physical pore parameters were necessary to explain the
changes in the strain between diIIerent samples. In this chapter, the method oI extracting
the pore parameters in the gas sorption method and strain on the sample by x-ray
scattering methods is discussed. In general, the gas sorption method is used Ior various
measurements and the ones used in this study are discussed brieIly. Similarly in x-ray
scattering the necessary theory is discussed brieIly with the applications in the study.
3.2. Gas sorption Method
This method is simple and economical to extract the structural parameters oI
porous material. This analysis is done with the aid oI computer and complex equipment,
which reduces the work to placing the sample and pushing the button. This section has a
brieI discussion on the basic principles oI this technique and the methods oI data
extraction used in this study.
24
3.2.1. Adsorption
Adsorption has been used practically by humans Ior thousands oI years. ScientiIic
study oI adsorption was extensive during the late 19
th
century like Kayser
20
in 1881but it
has been known even hundred years beIore that. The large capacity oI porous solids to Iill
up gases has been known as early as 1771 by Eontana
21
. In early and mid 19
th
century, the
role oI surIace area and pores were known and established to explain the greater capacity
oI porous solids by Saussere
22
and Mitscherlich
23
. In the early 1916, Langmuir
24
proposed a semi-empirical model with isotherms. Later in 1938, the existing Langmuir
theory was improved to BET theory
25
, which has been successIul and improved later.
Adsorption phenomenon Iorms the basis oI this whole study as it induces the
capillary condensation and capillary action. Adsorption is a surIace based process in
which a thin Iilm oI Iluid is created on a surIace oI solid due to the van der Waals Iorce
between the atoms oI the Iluid and surIace. It diIIers Irom absorption as the latter
involves the whole volume oI the solid to dissolve inside the Iluid rather than only the
surIace. There are two types oI adsorption, physical adsorption (physi-orption) and
chemical adsorption (chemi-sorption).When the Iorce between the atoms oI the Iluid and
the surIace are due to van der Waals Iorce then it is physical adsorption and iI the Iorce is
due to chemical bonding then it is chemical adsorption. The adsorbing Iluid is known as
adsorptive
24
beIore adsorption and adsorbate aIter adsorption. The complementary
phenomenon is known as desorption, which is the return oI the adsorbate to adsorptive.
This phenomenon along with a Iew others is used to extract the structural pore
parameters.
25
3.2.2. Capillary Condensation
Capillary condensation is the process by which multilayer adsorption oI vapor
into the pore Iills the pore space with condensed liquid. The capillary oI the pore induces
condensation at a lower vapor pressure than the saturated vapor pressure oI the pure
liquid. The lower vapor pressure is due to the high van der Waals Iorce on the adsorptive
due to the pore (cylindrical here) structure oI the adsorbent. Van der Waals Iorce is
inclusive oI adhesive and cohesive Iorces. The attraction between the adsorptive and the
surIace is speciIically adhesive Iorce. The adhesive Iorce is the intermolecular attraction
between two diIIerent molecules and when the intermolecular attraction is between like
molecules it is called as cohesive Iorce. On a planar adsorbent the direction oI the
adhesive Iorce between the adsorptive (liquid) and adsorbent (solid surIace) is along the
closest distance between them as shown in Eigure 5. Inside a nanopore the adsorptive
experiences the adhesive Iorce on all directions as shown in the Eigure. The high
attractive Iorce decreases the energy oI the adsorptive lower than the energy oI the pure
liquid at the same vapor pressure. Thus the adsorptive condenses at a lower vapor
pressure inside a nanopore. During adsorption multilayer Iormation Iills up the whole
space oI the pore with suIIicient vapor pressure oI the adsorptive. During desorption the
layer recedes in a diIIerent degree due to the presence oI meniscus. The curved top
surIace oI the liquid is called as meniscus, which is discussed in the next section.
26
Figure 5. Adsorption and Capillary condensation.
3.2.3. Capillary action and the formation of meniscus
When a capillary is immersed in a liquid, the liquid in the capillary rises with
curved top surIace above the surIace oI the immersed liquid as shown in the Eigure 6.
Capillary action can be explained by adhesive Iorce, cohesive Iorce and surIace tension.
SurIace tension is the Iorce per unit length required to pierce through the surIace oI the
liquid. SurIace tension oI water at room temperature is 7.12 N/cm, which means a denser
1 cm long body applying less than 7.12 N on the surIace will Iloat on water.
The top curved surIace oI the liquid as shown in the Eigure 6 experiences both
adhesion and cohesion. The surIace molecules experience cohesive Iorce only on the
downward direction as there are no molecules above it. This imbalance results in a net
27
Iorce downwards, which causes the surIace tension. When the adhesive Iorces between
the capillary and the liquid are greater than the cohesive Iorces, the molecules near the
walls oI the capillary move upwards Iorming a curved top surIace in the liquid called the
meniscus (as shown in the Eigure). The upward pull does not breach the surIace tension
oI the meniscus hence the liquid under the meniscus is pulled up to height h. The height h
depends on the weight oI the liquid that can be liIted by the surIace tension.
Figure 6. Capillary action and the pressure at diIIerent points.
The upward Iorce due to the surIace tension is E
up
T (2a r), where T is the
vertical component oI surIace tension .
The downward Iorce due to the pressure is E
d
pgh(a r
2
), as the pressure due to
the water in the capillary is pgh.
0
1
28
At equilibrium the height risen can be calculated by equating the two Iorces,
which results as h2T/r.
The height oI the liquid raised is inversely proportional to the radius, hence
smaller capillary rises higher. The liquid rising through the capillary against gravity is
known as the capillary action. The height oI the liquid creates capillary pressure.
3.2.4. Capillary pressure
Capillary pressure is the pressure diIIerence on the meniscus between two
immiscible Iluids. It is the compensation in the pressure to keep the interIace between the
Iluids intact. The Iorces on the meniscus at equilibrium are as shown in the Eigure 6 then
the Iorce balance equation is as Iollows.
( ) = ( ) + (2 ) (1)
T is the vertical component oI surIace tension .
Rearranging the above equation we get,
= - =
2
=
2
(2)
This equation is called as the Law oI Laplace.
Also consider the various pressures P marked in the Eigure 6,
P
1
P
2
, since both are atmospheric pressure.
P
2
P, since there is no capillary action in the interIace. It implies P
1
P P
w
.
P P
w
pgh.
As P P
1
, Capillary pressure P
c
P
1
P
w
pgh.
So, iI the surIace tension is ,angle oI contact between the liquid and the capillary is 0
and height risen is h, as shown in the Eigure 6 then the capillary pressure is P
c
2cos0/r
29
pgh 2T/r. The capillary condensation pressure and capillary (pore) radius are correlated
in a Iunction known as Kelvin Equation, which will be discussed later. The discussions
(3.2.1-3.2.4) were reIerred Irom (ReIs. 1,26).
3.2.5. Isotherms
It was noted earlier that during adsorption (desorption) the adsorptive Iorms a
layer on the solid surIace. The amount oI adsorptive which turns to adsorbate at a
particular vapor pressure reveals a great deal oI inIormation. This leads to adsorption and
desorption isotherms. An isotherm is a plot oI quantity (volume) oI gas adsorbed
(desorbed) at a constant temperature by a solid surIace as a Iunction oI relative vapor
pressure. The relative vapor pressure is the ratio oI the actual vapor pressure oI the
adsorptive (gas) to the saturated vapor pressure oI the adsorbate (liquid). The shape oI the
plots reveals a great deal oI inIormation about the adsorption system. The Iollowing six
Iorms oI plots describe pores oI diIIerent sizes and structure.
Figure 7. Types oI adsorption isotherms: adsorption (solid line), desorption (broken line);
iI there is no change in desorption line Irom adsorption line then it is not represented
separately.
29
3.2.5. Isotherms
separately.
29
3.2.5. Isotherms
separately.
30
This study is mainly based on mesopores so only the Type IV isotherm is
discussed. The nonporous isotherm (Type II) has the same general shape as a porous
isotherm but the intermediate rise is sharp. The adhesive Iorces experienced by the
adsorptive atoms increase when they are attracted by the adsorbent in more than one
direction such as inside a pore as discussed earlier. The increase in attraction decreases its
energy, which results in capillary condensation. Due to the capillary condensation, the
amount oI liquid inside the pore is more even at a lower relative vapor pressure. It
explains the sharper intermediate Ior porous isotherm than non porous isotherms. The
stark diIIerence between Type IV isotherms and others is the hysteresis. The rest oI the
isotherm types except Type V have overlapping adsorption and desorption isotherms.
Hysteresis in an isotherm is a signiIicant characteristic, which ascertains the
presence oI mesopores. An isotherm oI a nonporous material will not have hysteresis but
an isotherm without a hysteresis does not prove that it is Irom a nonporous material. The
hysteresis obviously indicates that the capillary evaporation is diIIerent Irom capillary
condensation in the mesoporous material. The shape oI the hysteresis reveals inIormation
about the shape oI the mesopores as shown in the Eigure 8.
31
Figure 8. Shape oI hysteresis in isotherms and the corresponding pore shapes
27
The enhanced adsorption in pores Iorms the basic principle Ior the gas sorption
method. A real porous material may have more than one particular size oI pores, which
varies the isotherms Irom the ideal but useIul inIormation can still be elicited.
32
Figure 9. Isotherm oI SBA-15 with nitrogen as adsorptive.
The isotherm plot oI SBA-15 shows interesting Ieatures, which reveals
inIormation about the sample. The presence oI hysteresis proves that the sample has
mesopores. The shape oI the hysteresis reveals the pore shape to be cylindrical Irom the
Eigure 5, which is characteristic to SBA-15. The relative vapor pressure at which
capillary condensation and evaporation occurs is known by reading x axis oI the plot. The
hysteresis is larger in SBA-15, which indicates that it takes lower relative vapor pressure
Ior capillary evaporation during desorption. This can be attributed to the presence oI
micropores, which needs a lower vapor pressure Ior evaporation.
32
32
33
Figure 10. Isotherm oI MCM-41 with nitrogen as adsorptive.
Similarly isotherm oI MCM-41 also reveals some inIormation about it. It is obvious that
it has cylindrical mesopores due to the presence oI hysteresis and its shape. The
hysteresis is smaller, due to the presence oI only mesopores. Another diIIerence is the
relative vapor pressure at which the capillary condensation and evaporation begins, which
is due to the diIIerence in the pore size between the samples. The above discussion was
based on (ReIs. 1, 11, 31).
3.2.. Kelvin Equation and B1H method
The BJH method is used Ior calculating surIace area, pore width and pore size
distribution in this study. The BJH method is based on Kelvin equation and it is popular
33
33
34
Ior mesopore analysis. This method was described by Barrett, Joyner and Halenda, hence
known as BJH method. The micropore area is Iound by using t-plot method and it is
exclusive oI the surIace area calculated by BJH method.
3.2.6.1. Kelvin Equation
The phenomenon oI capillary condensation is always observed in mesopores as
discussed earlier. The Iunction which correlates pore radius and the capillary
condensation vapor pressure is known as Kelvin equation(Appendix B), which is shown
below.
-
= - (S)
P
*
is the critical condensation pressure Ior the radius r
m
, P
o
is the saturated vapor pressure
oI the Iluid, V is the molar volume oI the condensate, r
m
is the mean capillary radius, R is
the gas constant and T is the temperature oI the adsorptive.
When the angle oI contact 0 90 Ior a mean capillary radius oI r
m
, the
condensation will occur iI the vapor pressure oI the adsorptive is greater than the
critical condensation pressure.
Another view is that the pore radius determines whether the condensation can
occur Ior the particular relative vapor pressure oI the adsorptive.
The second point is critical Ior the BJH method, Ior a particular relative vapor pressure
the necessary pore radius Ior capillary condensation to occur can be Iound. The Kelvin
equation sheds some light on the hysteresis seen on the isotherms discussed earlier. The
mean capillary radius Ior a pore, which is open at both ends, is given by two radii r
1
and
35
r
2
as shown in the Eigure. The materials used in the study has open ended pore, in these
pores the condensation is nucleated on the inner wall.
1
=
1
2
1
+
1
(4)
Figure 11. The meniscus with radii r
1
and r
2
inside the pore Iorming the core volume; the
thin layer t oI adsorbate (liquid) on the inner wall
During condensation the condensate builds layers inward to Iill the pore, which
implies that r
m
2r
1
because r
2
is inIinity as shown in the Eigure. Similarly during
evaporation r
2
r
1
r
m
, which is less than 2r
1
. The diIIerence in mean radius changes the
critical capillary condensation/evaporation and thus there is a hysteresis in Iilling and
emptying oI the pores.
In addition to the mean capillary radius, the thickness oI the Iilm oI adsorbate on
the pore must be accounted Ior. A pore will have a thin Iilm oI adsorbate on the pore wall
irrespective oI Iilling or emptying. This thickness oI the layer t is calculated using one oI
the three expressions shown below developed with varying level oI complexity. The
volume oI the adsorbate inside the thin Iilm Iilling up the pore is known as core volume
as shown in the Eigure 11.
r
2
r
1
36
So,
= + (S)
Where r
p
is the pore radius, r
m
is the core radius and t is the thickness oI the Iilm.
= S.S4 (6)
=
1S.99
u.uS4 -log
-
|24] (7)
= S.S4
-S
ln
-
|24] (8)
3.2.6.2 BJH method
The extraction oI the mentioned pore parameter is a complex series oI
calculations with some assumptions. In the BJH method, the pore shape is assumed to be
cylindrical which is good Ior this study but would skew the results Ior pores oI any other
shape. The other assumptions are the values oI surIace tension and molar volume in the
Kelvin equation, which might vary due to the presence oI only Iew molecules. The
deviations due to these assumptions are only small in the Iinal result and thus this method
is still popular.
The calculation is usually in the Iorm oI a table as shown in Eigure 12. The
desorption cycle oI the isotherm is usually used Ior this calculation. The isotherm gives
out two columns relating volume oI gas adsorbed and P/P
0,
the diIIerence between
subsequent data points would give the volume oI gas adsorbed(AV
g
) Ior that particular
37
decrease in P/P
0
. The product oI (AV
g
) with molar volume oI that liquid (here nitrogen)
would give the change in volume oI liquid (AV
l
) between that change in P/P
0
. The mean
radius Ior each P/P
0
can be calculated using the Kelvin equation and using the constants
Ior nitrogen. Similarly the thickness oI the layer can be calculated Ior each P/P
0
by using
one oI the equations (6, 7 and 8). Now by using the equation (5), the core radius can be
calculated. The thickness decrease At Ior each P/P
0
can be Iound by the diIIerence oI
thickness oI the layer calculated Ior subsequent P/P
0
. This volume lost due to this
thickness is the product oI surIace oI the Iilm AS and the thickness decrease At. Now, the
volume oI liquid lost can be calculated as,
A = + A A (9)
It is obvious that,
= (1u)
By substituting the value oI l Irom equation9 to equation10, the pore volume can be
calculated.
= (A - (A A )) (11)
Now with volume oI pore, it is simple to calculate the surIace area S using mensuration
Iormula Ior a cylinder.
38
Figure 12. The table oI BJH method calculation (top) Ior SBA-15, The plot pore volume
vs pore width (bottom) showing the pore size distribution Ior SBA-15.
39
In the path towards the calculation oI volume the pore radius (r
p
) has been calculated. The
pore size distribution is estimated by plotting pore volume and pore radius. The details oI
the process are explained in |29|.
Figure 13. The plot oI pore volume vs pore width showing pore size distribution Ior
MCM-41.
40
3.2.6.3 t-plot method
A plot oI volume adsorbed V
a
and thickness oI the adsorbed layer t is known as t-plot.
This plot varies between materials and microporous materials show a unique shape. This
uniqueness is used to estimate the micropore area in the material. This method is based
on BET theory. The details oI the process are explained in |29|.
The discussion in sections 3.2.6.1-3 were based on (ReIs. 1, 11, 28).
3.3. X-ray scattering method
In this study, an innovative method has been devised by combining the wide angle
x-ray scattering (WAXS) method and capillary action oI mesoporous material to
calculate the elastic modulus. The small angle x-ray scattering (SAXS) data has already
been used to extract the modulus in earlier works
9,10
. A similar experimental method Ior
SAXS was used here but the interpretation oI the extracted strain and the calculation oI
the modulus were modiIied to get a more accurate estimation. The changes suggested to
the earlier works were validated by examining the various Iorces due to capillary
condensation on the porous material, which has been discussed in the Iollowing section.
Extracting the strain by WAXS and calculating the modulus oI the porous material has
not been used beIore. The theory oI x-ray scattering with respect to this study will be
brieIly discussed in this section along with the use oI capillary action as stress. The
section begins with a brieI explanation about the mechanical parameters used in this
study.
41
3.3.1. Mechanical parameters
The mechanical properties that are extensively used in this study are elastic
modulus and Poisson`s ratio. The elastic modulus oI a material is deIined as the ratio oI
the applied stress P to the strain c in the same direction as in equation12. Stress is the
Iorce applied per unit area and strain is the deIormation oI the material due to that stress.
Modulus has the same dimensions as the pressure and it is measured in the units oI
gigapascals (GPa) in this study. In a macroscopic material it is possible to apply a known
stress and directly measure the deIormation oI the material optically or any other suitable
method and calculate the modulus. In a nanoporous material it is diIIicult to do the same,
so the capillary action oI water is used as the stress and the x-ray scattering method is
used to measure the strain.
= (12)
Usually a solid stretched in one plane will contract in the other perpendicular
planes and vice versa. Poisson`s ratio is the ratio between the strains in the plane
perpendicular to the applied stress and the direction oI the applied stress. The Poisson
ratio is the Iactor by which the perpendicular strain can be estimated Irom the strain in the
direction oI the applied stress. II the material is not isotropic the poisson`s ratio will have
three diIIerent values Ior diIIerent sets oI planes. This porous silica scaIIold in these
samples is considered to be isotropic with the same poisson`s ratio as the bulk silica
(v0.17). This assumption was arrived at aIter studying the same Ior honeycomb
mechanics and eliminating that due to the diIIerence in the direction and the points at
42
which the Iorces are acting here
29
. Hence the silica scaIIold is similar to a thin silica
structure so it can be considered as bulk silica.
= -
( )
( )
(1S)
When the poisson`s ratio is isotropic then the strain in each direction can be expressed as,
=
1
( - + )
=
1
( - ( + ))
=
1
( - + ) (14)
E is the young`s modulus and it is the same in all direction iI the material is
isotropic, o is the stress in the direction oI the subscript and v is the poisson`s ratio. These
expression will be used later to express the measured strain and calculate the young`s
modulus oI the material. This section was reIerred Irom (ReIs. 29, 30).
Figure 14. Stresses and strains in the three planes.
42
29
= -
( )
( )
(1S)
=
1
( - + )
=
1
( - ( + ))
=
1
( - + ) (14)
42
29
= -
( )
( )
(1S)
=
1
( - + )
=
1
( - ( + ))
=
1
( - + ) (14)
43
3.3.2. Capillary action of water as stress
The usual method Ior calculating this modulus Ior a macroscopic material is to
apply a known stress on the material in one direction and measuring the strain on the
same direction due to the stress. It is diIIicult to apply stress on a nanopore, so the
capillary action oI water in a pore was used to simulate the applied stress.
The relative vapor pressure (P
*
/P
o
) oI water is called as relative humidity (RH). In
this document the RH is speciIic term used in the place oI relative vapor pressure. The
RH around the sample is varied to control the amount oI water inside the pore, which
varies the magnitude oI the stress. During the adsorption, when the RH is increased Irom
0, water begins to adsorb to the inner surIace oI the pore wall. The thickness oI this
layer oI water increases as the RH is Iurther increased until a critical value. At this
critical value, the thick layer Iuses in the lengthwise middle oI the pore to Iorm a
meniscus and this meniscus moves rapidly to the pore entrance with increase in RH. This
rapid increase in the amount oI water in the pore is due to capillary condensation which
was discussed earlier. A Iurther increase in the RH decreases the curvature oI the
meniscus with very little change in the amount oI water inside the pore. In this study the
converse oI the above is used in the x-ray scattering experiments, which is desorption and
capillary evaporation.
Note:- RH and the P/P
o
are interchangeable as the Iluid used here is water and both the
notations are used here.
44
Figure 15. Various levels oI water in the pore with the increase oI RH
The amorphous silica Iorming the porous structure is reIerred to as a silica
scaIIold. The Iorces applied on the silica scaIIold by water are due to the surIace tension
and the Laplace pressure. SurIace tension has been discussed earlier and the action oI
surIace tension on the pore will be discussed here. There are three diIIerent surIace
tension components in this system, solid-liquid, liquid-vapor, solid-vapor as shown in
Eigure 16. It is intuitive to consider the
SL
(surIace tension solid-liquid) as the inIluence
oI tangential Iorce but it is the combination oI all the surIace tension which inIluences it.
The tangential Iorce on the silica scaIIold by water is the adhesive Iorce between them.
The normal Iorce arises Irom the liquid vapor interIace oI the meniscus. The tangential
component is
LV
(1cos0), which is derived below. The subscripts L, V, S represents
liquid, vapor, solid respectively.
44
SL
component is
LV
44
SL
component is
LV
45
Consider a bulk liquid and solid, each oI which are stripped into two separate
parts in vacuum. The energy necessary to strip these two bulk entities are the adhesive
Iorces A
LL
(liquid-liquid) and A
SS
(solid-solid) respectively. The new surIaces will have
surIace tension 2
LV
A
LL
(Iactor 2 is due to the two separated parts) and 2
SV
A
SS
and
when the separated liquid and solid part are joined together the adhesive Iorces between
solid and liquid will reduce the surIace energy. So,
= + - (1S)
The Iorce on the solid is A
SL
,as discussed previously, can be Iound by rearranging
the above equation and using Young`s law Ior the equilibrium contact angle.
= - (Young`s law) (16)
= + - = (1 + ) (17)
Thus the tangential Iorce on the solid arises Irom the interaction between the solid and
liquid which is given by adhesive Iorce A
SL
which has been derived to be
LV
(1cos0).
This relation Ior tangential component has been conIirmed with DET calculation
33
. The
normal component
LV
sin0 arises Irom the reaction oI the solid to the Laplace pressure
and has been conIirmed by DET calculation
33
. The resultant Iorce due to these
components is always into the liquid in the direction oI halI oI the contact angle 0. It is to
be noted these Iorces on the solid are due to the liquid in the core volume, (i.e.) the liquid
excluding the layer oI liquid in the wall. Hence the components on the solid due to liquid
in the core volume are
LV
(1cos0) and
LV
sin0. This normal component
LV
sin0 acts
only at the meniscus so it is neglected considering the other Iorces.
46
The Iorce exerted by a Ilat Iilm oI liquid on the solid will be in the normal
direction to the surIace. This Iorce arises due to the curvature oI the porewall
33
. This
Iorce can also be explained as the molecular interaction at the solid-liquid interIace.
There will be an attractive Iorce experienced by the solid molecules. This attractive Iorce
will be balanced by repulsive Iorce inside the liquid Iar Irom the interIace. At the curved
solid-liquid interIace the repulsive Iorces between the molecules become zero and the
unbalanced attractive Iorces pull the solid towards the liquid due to pressure diIIerence oI
LV
(1cos0)/r
32
. This stress is in the normal direction and towards the center oI the pore.
This stress is present along the length oI the pore and hence it is considered in estimating
the total stress.
The other Iorce on the solid by liquid is the Iorce due to Laplace pressure oI the
meniscus. It is critical to include this Iorce into the estimation oI the total Iorce on the
solid. The curved interIace between two phases means that there is a pressure diIIerence
between them. At equilibrium this pressure diIIerence is balanced by the surIace tension
oI the interIace
34
. This can be expressed as,
- =
2
(18)
The radius oI curvature is r and the subscripts v and l denote vapor and liquid
respectively. II the radius oI curvature oI interIace is non-spherical then the curvature part
oI the equation will change to two radii in perpendicular planes as seen in the Eigure 11.
- = (
1
+
1
) (19)
47
When the relative humidity is 100 it could be thought that there is no diIIerent
phase and the pressure diIIerence as zero. The decrease in relative humidity increases the
curvature oI the interIace and pressure diIIerence between increases. The direction oI the
pressure is perpendicular to the surIace oI the meniscus. This Iorce applies to the whole
length oI the pore. According to Pascal`s law, the pressure exerted on a conIined liquid
transmits equally on all direction and because oI this phenomenon the Laplace pressure
on the interIace spreads throughout the liquid. This Iorce on the solid is outwards and
normal throughout the length oI the pore until the presence oI meniscus in the pore. AIter
the disappearance oI the meniscus the Iilm oI water on the inner surIace oI the wall
contributes to the Iorce in the normal direction but it is now due to the surIace tension
only as discussed earlier.
In the previous section, the Kelvin equation(Appendix B) has been discussed with
respect to the gas sorption. The Kelvin equation also represents the Laplace pressure due
to the presence oI a meniscus.
= ;
1
=
1
2
1
+
1
(2u)
The variables represent the same as beIore. It is evident Irom the above equations that the
Kelvin equation relates the Laplace pressure to the natural logarithm oI relative vapor
pressure. This relation provides an easier way to estimate than measuring the surIace
tension and wetting angle in experiment. By rearranging, the equation Ior Laplace
pressure P
L
becomes as Iollows.
48
= =
The above expression is vital and will be used in the calculation oI modulus in the results
section.
component(red), Normal component(blue),Eorce due to Laplace pressure(yellow);The
direction oI surIace tension on each interIace (red solid arrow);EIIective Iorces on the
solid(right).
These eIIective stresses in each direction will be used in the calculation oI the
modulus. The discussion in this section was based on (ReIs. 32, 33, 34)
48
= =
section.
solid(right).
48
= =
section.
solid(right).
49
3.3.3. X-ray scattering
This microscopic technique works under the principle oI interIerence oI x-rays
and scattering oI X-rays. This varies Irom optical microscopy in the reconstruction oI the
image aIter interaction oI the incident waves with the sample and the structure detail. The
lens system used on the reconstruction in optical microscopy is replaced with
mathematical methods. In simple terms, it is the beam oI collimated x-rays incident on
the sample and scattered due to the electron density contrast oI the sample onto the
detector.
The scattered waves are recorded as such and reconstructed by mathematical
methods. This mathematical reconstruction has phase loss due to the way oI recording oI
the scattered waves. Hence the retrieval oI the shape and size distribution together is not
possible. The details oI the sample are average rather than unique. The scattering data oI
structures needs some inIormation oI the sample Irom other methods Ior proper
interpretation. Though there are some shortcomings, this method is preIerred due to the
Ilexibility in sample preparation such as in-situ and in-vivo observations and Ior the
average detail oI the whole sample. The sample preparations are usually none or simple,
and the sample are not damaged so this method is considered non-destructive. In this
study the eIIect oI capillary condensation on the pores is measured in-situ, thus x-ray
scattering is a relevant technique.
The two primary interactions oI x-rays with matter are absorption and scattering.
The absorption is the process in which the energy oI the incident x-ray photon is used up
by the atom to bump out an electron and a Iluorescent radiation emitted by the atom to
50
restore the original conIiguration. The absorption depends on the sample and the
wavelength oI the x-ray, and it must be minimized Ior a good scattering data. There are
two types oI scattering, Compton (Inelastic) and Rayleigh (Elastic) scattering. In the
inelastic scattering the incident x-ray photon loses some energy during collision with
electrons in the sample. In the elastic scattering the incident photon collides with
strongly-bound electrons and excites them to emit coherent waves. These coherent waves
interIere and produce the scattering pattern on the detector. The inelastic scattering
produces incoherent waves, which cannot produce any pattern so it would Iorm a
background noise.
The constructive and destructive interIerence oI the scattered x-rays depends on
the angle oI observation in the detector with respect to the incident x-ray, distance
between the atoms and the orientation oI the conIiguration oI atoms. The scattered x-rays
Iorm a pattern oI intensity variation in 20 scale. The interIerence pattern oI particular
arrangement oI particles will create identical pattern. II there is more number oI that
particular arrangement than the other then the interIerence pattern will have a higher
intensity. The distances in the pattern are measured with the quantity q which is
and also known as the scattering vector. The quantity q represents a length
in reciprocal space so its dimension is the inverse oI length. It is derived Irom the Bragg`s
law = 2 and = , where d is the distance between two consecutive planes in
the arrangement, 0 is the angle oI incidence and the wave-length oI the radiation as
shown in the Eigure.
51
Figure 17. The scattering oI x-rays Irom a planar arrangement oI particles
37
The equation oI scattering vector implies that the size oI the structure probed by
the x-rays inversely depends on the scattering angle. As q is in reciprocal space, smaller q
value means a larger value in real space and vice versa. Hence larger interplane distance
d has peaks in the smaller q values which correspond to the small scattering angle and
smaller interplane distance have peaks at larger scattering angle. This angle dependence
results in two types oI x-ray scattering technique, small angle x-ray scattering (SAXS)
and wide angle x-ray scattering (WAXS). When the scattering angle is Irom 0 to 10 it is
SAXS and this enables in probing structures (interplane distances) that are nanometer to
micrometer dimension. The detector is kept at a distance Iarther Irom the sample
depending upon the necessary resolution. When the scattering angle is larger than 10 it
is WAXS and this enables probing structures smaller than that studied in SAXS. The
detector is near the sample and the distance depends on the necessary resolution. The
necessary theory Ior the scope oI this study has been discussed in (ReI. 36).
52
When the interplane distances are ordered then it inIluences the intensity pattern
to peak at the 20 angle oI the respective distance. This peak is known as Bragg peak. The
maximum oI the peak gives that distance in q space and it is the inverse oI the interplane
distance in real space ( .The SAXS patterns oI the sample Ior two diIIerent
values oI relative humidity (RH) are combined in the Eigure below. The Iirst peak in the
SAXS represents the 10` plane oI the hexagonal arrangement oI the pores in the
reciprocal space as seen in the Eigure 19. This position oI the maximum oI the peak
corresponds to the interpore distance in real space. The real space distance can be
calculated Irom the position oI the peak as discussed earlier. The Bragg peak position oI
RH-54 shiIts towards the right, which is increasing in reciprocal space. In real space the
distance decreases, which means that pores are closer at RH54 than RH86. The
implication oI closer pores is the compression oI the porewall (silica scaIIold). Thus the
shiIt in peak position can measure the strain. The detailed discussion is presented in later
chapters.
53
Figure 18. Comparison oI SAXS patterns oI MCM-41 at 54 and 86.
The electron density contrast between the sample and its background must be
signiIicant Ior a good data. The intensity oI scattering pattern also depends on this density
contrast. The scattering pattern oI the background is usually collected beIore introducing
the sample and this pattern is subtracted Irom the pattern oI the sample. It is always good
to have as much high intensity as possible, which implies that the intensity oI the sample
should be greater than the background. In in-situ and in-vivo observations the intensity
variations can be used to detect the quantitative change in the composition oI the sample.
The x-rays collected on the detector are scattered Irom the electrons in the sample. The
intensity oI the pattern is given by,
(22)
P(q) is the Iorm Iactor, S(q) is the structure Iactor, v volume oI a particle, Ap is the
density contrast and I is the scattering intensity oI one electron. The Iorm Iactor reveals
the shape oI the particle and it is the pattern occurring due to the atoms in a particle. The
53
(22)
53
(22)
54
structure Iactor reveals the distances between the particle planes and it is the pattern
occurring due to inter-particle distances.
Another interesting Iactor in Eigure 18 is the change in the intensity between the
two patterns. This intensity diIIerence is attributed to the change in the amount oI water
in the pore. It can be inIerred Irom equation 22 that the intensity depends on the density
contrast. There are three media in the system, silica, water and air. The density contrast
between silica and air is obviously greater than it is between silica and water. Hence iI
there is more water in the system then the overall density contrast will be lower. The
amount oI water will deIinitely be greater at RH86 than RH54. This intensity
variation will be later used in determining the data points that must be used to calculate
the modulus.
The structures probed in the WAXS are smaller and usually on the order oI a
atomic scale. The Iorm Iactor mentioned in the above discussion becomes the atomic
Iorm Iactor at these scales. Some amorphous glass materials and liquids exhibit a peak in
WAXS and it is known as Iirst sharp diIIraction peak` (ESDP). ESDP represents an
intermediate range order in the system. The corresponding real space structure is still not
clearly determined.
The WAXS pattern is shown below Ior two diIIerent values oI RH, with the Iit
model as inset. Similar to SAXS, ESDP oI WAXS is also used to measure the strain. The
diIIerence in this strain is that it measures the strain oI the whole silica skeleton rather
than the one plane measured in SAXS. The peak position in WAXS is not as obvious as
SAXS because the ESDP is a combination oI two peaks. The two peaks represent
55
presence oI silica and water in the system. The ESDP is Iit with two asymmetric pseudo
voigt (APV) Iunctions to model the presence oI silica and water as shown in the inset oI
the Eigure. The algorithm Ior the Iit is modeled so as to simulate the change in the
amount oI water Ior each RH. The shiIt oI the peak oI silica APV is used to measure the
strain. These strain measurements will again be discussed in the Iollowing chapters.
Figure 19. Comparison oI WAXS patterns oI MCM-41 at 54 and 86.
The experiments in this study were conducted using an in-house x-ray scattering
source and also a synchrotron source. The in-house scattering apparatus uses an x-ray
tube with copper target to produce x-rays. The production oI x-ray in these is typical:
incidence oI electron on the target. Synchrotron sources use a diIIerent technique, where
x-rays are produced by accelerating electrons to relativistic speeds in a circular path. The
brieI discussion oI x-ray scattering in this section was reIerred Irom (ReI. 36).
55
55
56
CHAPTER 4: EXPERIMENT
4.1. Gas sorption experiment
Micromeritics Tristar II SurIace Area and Porosity System (Micromeritics
Instrument Corporation, USA) was employed to extract structural pore parameters such
as surIace area, pore width, micropore area, pore size distribution and sorption isotherms.
A test tube with about 0.2g oI the synthesized sample was loaded to the Micromeritics
degas system. During the degassing, sample was heated to 400C and Ilushed with
nitrogen. AIter degassing, the mass oI the degassed sample was accurately obtained and
the test tube was loaded into Micromeritics Tristar II SurIace Area and Porosity System.
The characteristics oI the sample were given as input into the application in the computer,
which controls the whole process. The sample was held in a liquid nitrogen bath and the
data were determined by the adsorption oI nitrogen and helium. Three samples can be
analyzed simultaneously and it takes about 15 hours Ior the whole process.
Porosity (right)
37
.
56
Porosity (right)
37
.
56
Porosity (right)
37
.
57
4.2. X-ray scattering experiment
4.2.1 SAXSess
SAXS and WAXS data were used to extract the strain on the pores due to
capillary action oI water as discussed earlier. SAXSess is a table-top x-ray scattering
system manuIactured by Anton Paar GmbH, Austria. This was employed to get the
SAXS/WAXS pattern with a homemade sample chamber which had provisions to control
and monitor the relative humidity (RH) around the sample pellet. The RH was controlled
by a humidity generator with distilled water as the Iluid and the actual RH in the chamber
was monitored with the sensor inside the chamber. There was a small diIIerence between
the set RH and the actual RH in the sample chamber and the actual RH value was always
considered Ior the data. The preliminary adjustments in SAXSess were made and it was
calibrated to the particular sample holder. The sample pellet was placed in the pellet
holder inside the sample chamber with ample surIace exposed Ior the scattering. The
sample chamber was then loaded into the SAXSess in the appropriate position. The
SAXSess was evacuated to 1atm with the vacuum generator which ran throughout the
experiment to maintain the vacuum. AIter the vacuum was attained the x-rays were
generated to impinge on the sample. The relative humidity inside the chamber was varied
Irom 100 to 0 in steps oI 5 with 1 hour Ior each step. The scattered x-rays were
collected using an imaging plate. The imaging plate records the x-rays by locking the
electrons in it to a metastable state and it was read by illuminating with visible light in a
reader. Hence, aIter recording each step the imaging plate was careIully transIerred into
58
its reader in the dark. The data Irom the imaging plate transIers to a computer as a 2D
data and it is converted to 1D by an application. In SAXSess only the WAXS data was
used to estimate the strain. The SAXS pattern was acquired separately Ior 10 min at RH
oI the room and was used to determine the quality oI the sample and the interpore
distance. During the recording oI the WAXS a lead block was used to protect the imaging
plate Irom over exposure. The exposure oI high intensity oI the SAXS Ior one hour
would damage the imaging plate. The lead block prevented the high intensity part oI the
pattern Irom reaching imaging plate. The WAXS peak was Iit using WinXAS and its
parameters was extracted Ior Iurther analysis. The WinXAS is developed by Thorsten
Ressler Ior x-ray adsorption spectroscopy studies. The wavelength oI x-rays used was
1.542A which is the k-alpha line oI copper. There was approximately a 20 min gap
between setting the RH Ior the particular step and the beginning oI the exposure oI x-rays
which gave enough time Ior RH to stabilize inside the chamber.
The 1 D data Irom the computer was Iit with WinXAS soItware to extract usable
parameters. The maxima oI WAXS peaks were extracted by Iitting Iunctions in the 1D
data. An algorithm was created Ior each sample and it was run Ior the dataset oI each
sample. The maxima were not directly read because the peaks in the raw 1D data are
combinations oI more than one Iunction. In WAXS, a pseudo voigt Iunction representing
silica and a higher degree polynomial representing water are Iit to extract the proper
position oI maximum oI the peaks due to silica. In SAXS data the maximum oI the Iirst
Bragg`s peak was directly Iound and used to estimate the interpore distance.
59
AIter the synthesis oI the sample, the SAXS pattern was collected in SAXSess to
assess sample quality. II the pattern shows the proper peaks and ordering then the sample
is subjected to the gas sorption method to extract the pore parameters. AIter that the strain
due to capillary action was measured using the WAXS pattern as discussed above.
and the converted 1 D data (right bottom).
4.2.2. Synchrotron
Apart Irom using SAXSess, the same study was conducted in the synchrotron at
Argonne National Laboratory to justiIy and conIirm the results with better quality oI data.
The sample pellets used were similar to the ones used in SAXSess. The pellet was cut
into a smaller piece which would Iit in the synchrotron sample holder. The sample holder
had an inlet and outlet Ior the circulation oI air with the controlled RH. The same
humidity generator mentioned above was connected to the inlet and the same humidity
sensor was placed at the outlet to measure the actual RH. Due to the high energy oI the
59
4.2.2. Synchrotron
59
4.2.2. Synchrotron
60
synchrotron x-rays the exposure time was reduced to 10 seconds Ior each step. The steps
were similar to the SAXSess experiment, RH was varied Irom 100 to 0 with 5 steps
and noting the actual RH Ior the data. The wait time Ior the RH to stabilize was set to 10
min aIter observing no diIIerence between the patterns oI 10 and 15 min stabilizing time.
The SAXS and WAXS were obtained at the same time and sample`s parameters were
extracted in a similar way as above using the WinXAS. The wavelength oI the x-rays in
synchrotron was 0.2034A.
The Iitting oI this SAXS and WAXS was diIIerent. In SAXS data, an exponential
Iunction representing the decrease oI intensity with the increase oI q, a polynomial
Iunction representing the background due to the inelastic collision oI x-rays and
signiIicantly the asymmetric pseudo voigt (APV) Iunction representing the peaks were Iit
to extract the proper position oI the peaks. Sometimes the range oI q considered Ior the
data is small, so the exponential Iunction is avoided to create a better algorithm. In
WAXS, two APV Iunctions representing silica and water were Iit to extract the proper
position oI maximum oI the peak due to silica. The position oI the APV representing
water was Iixed at the value near to the peak oI pure water. In the Iit algorithm Ior the
WAXS data, the amplitude oI the APV representing water reduced with decrease oI RH
and this automatically simulates the decrease oI water in the system with decrease oI RH.
4.2.3. Comparison between SAXSess and synchrotron data
The x-ray scattering experiment was perIormed with two diIIerent sources as
mentioned in the experimental section. The quality diIIerence between the SAXSess and
synchrotron data was signiIicant due to the energy oI the source, collimation and the
detector. The detector used in SAXSess was an imaging plate, which traps electrons
61
excited by incident x-rays in it to a metastable state known as E-trap
38
. The trapped
electrons were brought to the ground state by illuminating with visible light. The energy
released by the electrons is radiated as Iluorescent radiation which is collected and
processed by a computer algorithm to give a 2d plot. In the synchrotron, the detector was
a wire detector called as Pilatus. This basically has a matrix oI electronics on the screen
representing each pixel. The wire detector has shorter data retrieval time and can acquire
higher intensity without any damage. Hence the exposure time has no constraint. The
imaging plate tends to reach a limit Ior the intensity it can record.
The source in the synchrotron is a point source and the source in SAXSess is a
line source. In a point source, only a small part oI the sample is exposed and the 2d
pattern has concentric circles. Eor the line source a large portion oI the sample is exposed
as the x-ray beam is conIined in only one direction. The 2d pattern has broader concentric
ovals
38
. The broadening is the result oI the larger area oI exposure oI the sample and it
causes smearing oI the pattern
38
. The larger area exposure decreases the exposure time
Ior a particular intensity with same energy. Thus the point collimation was not used in the
SAXSess instrument. In the synchrotron the energy oI the x-ray is higher than in
SAXSess and is suIIicient Ior point collimation to produce a higher intensity than the
SAXSess without smearing.
The intensity diIIerence between the SAXS peak and WAXS peak is an indication
Ior the quality oI the pattern. The intensity diIIerence between them must be larger Ior a
better pattern. In the Eigures below, the pattern Irom the SAXSess and the synchrotron
has been shown. The synchrotron pattern has a larger diIIerence between SAXS and
WAXS. Although the data collected Irom the SAXSess enabled in deducing the trend oI
62
the strains oI the sample, the error in the data was large. All oI the data presented in the
work are Irom synchrotron, which was more reliable Ior the actual calculations.
intensity oI the SAXS peak (top); The arrow indicate the intensity oI the WAXS peak
(bottom).
62
(bottom).
62
(bottom).
63
part oI SAXS peak (top arrow) and the WAXS peak (bottom arrow).
63
63
64
CHAPTER 5: RESULTS AND DISCUSSION
The data and the interpretation oI the each experiment are discussed in separate
sections and Iinally summarized.
5.1. Gas-sorption method:
The speciIic surIace area, pore width, micropore area, pore size distributions and
isotherms are the data extracted Irom this method. These data are essentially used to
determine the quality oI the sample beIore undertaking the X-ray scattering experiments.
Table 1
Phvsical pore parameters extracted from gas-sorption method
Sample SurIace Pore Porewall Micro pore
Area (m
2
/g) width (A) thickness (A) Area (m
2
/g)
MCM-41 AS` 1082.83 26 15 0
MCM-41 AN` 1132.88 24 16 0
SBA-15 AS` 367.90 60 48 147.90
SBA-15 AN` 368.44 59 48 130.19
The surIace area, micropore area, pore width are directly extracted Irom the gas-
sorption method as discussed earlier. The pore wall thickness is the diIIerence between
the interpore distance at stress Iree conIiguration calculated Irom SAXS and the pore
65
width. These data will be used later to explain the elastic modulus variation between the
samples.
5.2. X-ray scattering technique:
There were two scattering patterns produced by these samples, SAXS and WAXS
as discussed earlier. The position oI the Iirst Bragg`s peak oI SAXS, Iound by Iitting the
data, corresponds to the interpore distance. It was plotted against RH to view the
variation oI that distance. It must be noted that the y axis is in reciprocal space.
Figure 24. Top leIt: SAXS peak position vs RH plot Ior MCM-41 AS` ;Top right: SAXS
peak position vs RH plot Ior MCM-41 AN`; Bottom leIt: SAXS peak position vs RH
plot Ior SBA-15 AS`; Bottom right: SAXS peak position vs RH plot Ior SBA-15`AN.
65
samples.
65
samples.
66
The Bragg`s peak position actually gives the distance between the 10` planes, by
using simple geometry the interpore distance can be calculated as shown in the Eigure.
SAXS the interpore distance is calculated by using the perpendicular triangle. The area
Iilled with red represents the porewall.
These interpore distances are in the x-y plane as shown in the Eigure 25. It must be noted
that the position is in the units oI inverse oI length. In MCM-41, at high RH the interpore
distance is higher than it is at stress Iree interpore distance oI the lowest RH, which
implies that the pore wall is stretched at those RH. The lowest RH with almost no water
in the pore is considered as the stress Iree conIiguration. Gradually the inter pore distance
decreases with reducing RH, which implies that the pore wall is compressed. The
66
66
67
compression continues beyond the stress Iree conIiguration. Eurther reduction in RH the
pore wall relaxes to the stress Iree conIiguration.
In SBA-15, it is more complicated than the above explanation. There are two
series oI compression and tension similar to the one observed in MCM-41 as explained
above. The Iirst one occurs when the meniscus is at the entrance and the second occurs
during the capillary evaporation. The second one can be attributed to the eIIect oI
micropores due to the continued presence oI water in them even when the mesopores are
emptying.
position vs RH plot oI MCM-41 AN`; Bottom leIt: WAXS peak position vs RH plot oI
SBA-15 AS`; Bottom right: WAXS peak position vs RH plot.
67
emptying.
67
emptying.
68
The WAXS data corresponds to the distance in atomic scale. Similar to the
SAXS plot, the ESDP position oI WAXS aIter the Iit is plotted against RH. The ESDP
peak position distances are on the atomic scale and their variation represents the average
change in those distances in all planes.
In MCM-41, the distance at high RH is almost same as the stress Iree distance at
the lowest RH. The whole sample begins to compress with reducing RH. At high RH the
interpore distances in x-y plane is at compression but the atomic scale distances in the
whole material is stress Iree, which is a very interesting result. This would imply that the
cumulative atomic distances must extend in the z plane in the same amount as the
cumulative compression in the atomic distances due to the compression oI porewall in x-
y plane (observed in SAXS). The highest compression occurs aIter the beginning oI the
capillary evaporation. Eurther reduction in RH, the distances expand to the stress Iree
conIiguration. In this study a new technique is developed to use this distance variation to
estimate the strain in all planes.
The Kelvin equation and Laplace pressure hold true only till the meniscus is
present at the pore entrance during desorption. The elastic modulus oI the sample is
calculated using the Kelvin equation hence the strain must be extracted only with the data
beIore the capillary evaporation. The variations in density contrast correlate the amount
oI water present in the pore as discussed earlier. The amplitude oI the Bragg`s peak is
plotted against the RH to visualize the change in amount oI water. These plots can be
studied to determine the data that must be used to estimate the strain to calculate the
elastic modulus using Kelvin equation.
69
The line represents that the rate oI water loss during capillary evaporation.
69
69
70
Figure 28. The SAXS intensity and the SAXS strain oI MCM-41 AS` are plotted
O.O O.5 1.O
O.5
1.O
1.5
2.O
2.5
3.O
3.5
lntensity_SAXS
Strain_SAXS
RH
l
n
t
e
n
s
i
t
y
(
a
r
b
.
u
n
i
t
s
)
-O.OO4
-O.OO3
-O.OO2
-O.OO1
O.OOO
O.OO1
O.OO2
O.OO3
S
t
r
a
i
n
_
S
A
X
S
71
Figure 29. The SAXS intensity and the SAXS strain oI MCM-41 AN` are plotted
O.O O.1 O.2 O.3 O.4 O.5 O.6 O.7 O.8 O.9 1.O
O.5
1.O
1.5
2.O
2.5
3.O
lntensity_SAXS
Strain_SAXS
RH (%)
l
n
t
e
n
s
i
t
y
(
a
r
b
.
u
n
i
t
s
)
-O.OO3
-O.OO2
-O.OO1
O.OOO
O.OO1
O.OO2
S
t
r
a
i
n
_
S
A
X
S
72
Figure 30. The SAXS intensity and the SAXS strain oI SBA-15 AS` are plotted together
to deduce the data points that are used to calculate the elastic modulus.
O.O O.1 O.2 O.3 O.4 O.5 O.6 O.7 O.8 O.9 1.O
5
1O
15
2O
25
3O
35
lntensity_SAXS
Strain_SAXS
RH
l
n
t
e
n
s
i
t
y
_
S
A
X
S
-O.OO1O
-O.OOO5
O.OOOO
O.OOO5
O.OO1O
O.OO15
S
t
r
a
i
n
_
S
A
X
S
73
Figure 31. The SAXS intensity and the WAXS strain oI SBA-15 AN` are plotted
O.O O.1 O.2 O.3 O.4 O.5 O.6 O.7 O.8 O.9 1.O
5
1O
15
2O
25
3O
35
lntensity _SAXS
Strain_WAXS
RH
l
n
t
e
n
s
i
t
y
(
a
r
b
.
u
n
i
t
s
)
-O.OO4
-O.OO3
-O.OO2
-O.OO1
O.OOO
O.OO1
O.OO2
S
t
r
a
i
n
_
W
A
X
S
74
Figure 32. The amplitude oI SAXS Iirst Bragg`s peak vs RH plot Ior SBA-15 AS`. The
lines represent that the rate oI water loss has two diIIerent rates during the capillary
evaporation.
The strain Ior the samples were plotted together to enable better comprehension oI
the discussion. The estimation and plot oI the strain is discussed next in this section. The
relatively Ilat portion oI the curve in the plots at high RH corresponds to little or no
change in the amount oI water. This region marks the presence oI the meniscus at the
pore entrance. The strain is extracted Irom this range oI RH to calculate the elastic
modulus. Beyond that region the meniscus moves inside the pore with the reducing RH.
This movement oI meniscus reduces the amount oI water inside the pore and it also the
sign oI capillary evaporation. In SBA-15 the range oI RH at which capillary condensation
occurs has two diIIerent slopes unlike the MCM-41 which has only one as shown in the
O. O O .1 O. 2 O .3 O . 4 O. 5 O . 6 O. 7 O .8 O. 9 1 .O
5
1O
15
2O
25
3O
S
A
X
S
_
l
n
t
e
n
s
i
t
y
R H
75
above Eigures. This is attributed to the presence on micropores, during capillary
condensation in mesopores the micropores are still Iilled with water. The rate oI loss oI
water is diIIerent Ior micropores. It takes a lower RH Ior the water in micropores to
evaporate.
AIter Iitting the curves and extracting the position oI the maxima, the strain Irom
both SAXS and WAXS can be calculated by the Iollowing Iormula by using the peak
shiIt.
=
( )
( )
- 1 (23)
c is the strain, p(0) is the position oI the maximum Ior zero stress which is the
lowest humidity data point considered as reIerence state, p(RH) is the position oI the
maximum Ior every other RH data points. The strain is then plotted against the natural
logarithm oI the RH as shown in the graphs below.
76
MCM-41AS`. The trendline corresponds to data points(black) beIore the capillary
evaporation. The inset shows the slope and the error in the trendline.
-2.5O -2.25 -2.OO -1.75 -1.5O -1.25 -1.OO -O.75 -O.5O -O.25 O.OO
-O.OO3
-O.OO2
-O.OO1
O.OOO
O.OO1
O.OO2
O.OO3
O.OO4
S
t
r
a
i
n
_
S
A
X
S
ln(RH)
Equaticn
y = a + b*x
Weight Nc Weighting
Residual Sum
cf Squares
9.32953E-8
Pearscn's r O.99864
Adj. R-Square O.99695
Value Standard Errcr
Strain_SAXS lntercept O.OO415 8.23879E-5
Strain_SAXS Slcpe O.OO921 1.69818E-4
77
MCM-41AN`. The trendline corresponds to data points(black) beIore the capillary
-2.5O -2.25 -2.OO -1.75 -1.5O -1.25 -1.OO -O.75 -O.5O -O.25 O.OO
-O.OO3
-O.OO2
-O.OO1
O.OOO
O.OO1
O.OO2
O.OO3
O.OO4
S
t
r
a
i
n
_
S
A
X
S
ln(RH)
Equaticn
y = a + b*x
W eight Nc W eightin
Residual Sum
cf Squares
3.O9O91E-8
Pearscn's r O.99935
Value Standard Errc
Strain_SAXS lntercept O.OO228 3.73O4E-5
Strain_SAXS Slcpe O.OO63 7.572E-5
78
SBA-15AS`. The trendline corresponds to data points(black) beIore the capillary
-2.5O -2.25 -2.OO -1.75 -1.5O -1.25 -1.OO -O.75 -O.5O -O.25 O.OO
-O.OO2
-O.OO1
O.OOO
O.OO1
O.OO2
O.OO3
S
t
r
a
i
n
_
S
A
X
S
ln(RH)
Equaticn
y = a + b*x
Weight Nc Weighting
Residual Sum
cf Squares
9.463O4E-7
Pearscn's r O.95O19
Strain_SAXS lntercept O.OO38 4.71597E-4
Strain_SAXS Slcpe O.O11O8 O.OO182
79
SBA-15AN`. The trendline corresponds to data points(black) beIore the capillary
Similar to the earlier discussion with distances oI the peaks, the strain also reveals
the same compression and tension at various stages. In MCM-41 the strain is positive at
high RH and changes to negative with the decrease oI RH to its lowest value just beIore
capillary evaporation. The physical interpretation is, the porewall is at highest tension at
the highest RH and begins to relax during desorption to the reIerence stress Iree
conIiguration. It contracts below the reIerence stress Iree conIiguration and reaches the
highest compression just beIore capillary evaporation. During the capillary evaporation
-2.5O -2.25 -2.OO -1.75 -1.5O -1.25 -1.OO -O.75 -O.5O -O.25 O.OO
-O.OO2
-O.OO1
O.OOO
O.OO1
O.OO2
O.OO3
S
t
r
a
i
n
_
S
A
X
S
ln(RH)
Equaticn
y = a + b*x
W eight
Nc W eighting
Residual Sum
cf Squares
7.28482E-7
Pearscn's r
O.86O28
Adj. R-Square
O.65344
Strain_SAXS
lntercept O.OO223 5.51429E-4
Strain_SAXS
Slcpe O.OO73 O.OO25
80
the pore relaxes to stress Iree conIiguration. AIter the breaking oI the meniscus the pore
contracts to the stress Iree conIiguration.
In SBA-15 at high RH it is similar to MCM-41 but the lowest compression is
reached at relatively higher RH than MCM-41. During capillary the evaporation, the
porewall begins to stretch to a point and again compresses to the lowest compression.
Eurther reduction in RH relaxes the porewall to the stress Iree conIiguration. The
variation in the strain during capillary evaporation is due to the presence oI water in the
micropores at these ranges oI RH and they emulate a similar mechanism oI mesopores
beIore capillary evaporation.
The strain extracted Irom the SAXS data is in the plane perpendicular to the
channel oI the pore. According to the earlier works by Prass
9
and Gor
10
, the strain was
presented as
=
1
-
(24)
and
=
1
(- +
-
+ ( -
-
)) (2S)
respectively. All the symbols represent the same as beIore and P/P
0
RH. It is evident
Irom the earlier arguments and the literature
32,33
there are Iorces acting on the solid other
than the Iorce due to Laplace pressure which is the natural logarithm term in the above
expression (also discussed earlier). The Iorces arising Irom the surIace tension eIIects
were not considered in equation24. In the equation 25, the eIIect oI the tangential
component oI surIace tension was not considered.
81
According to the earlier discussion it can be inIerred that there are other stresses
involved in this system. The Iorces are summarized here based on the earlier arguments.
Table 2
Summarv of the stresses acting on the porewall in each plane
Stress Direction Stress Stress term
Normal (X-Y Plane) o
x
, o
y
2 +
Tangential (Z Plane) o
z
- +
Due to the ordering oI the pores and the symmetry oI the Iorces here, the stress on
both x and y direction could be considered same (o
x
o
y
). The equation 14 represents the
total strain in each plane in relation to the stress and poisson`s ratio. Now by substituting
the stresses into that equation we get,
=
-
(2 - S ) + (26)
At high RH the pores are Iarther apart Irom each other in x-y plane (normal to the
pore channel), which also mean the porewall is stretched. The stress due to the surIace
tension oI thin layer oI water on the inner wall pulls the pore wall toward the center oI the
pore. The tangential compression also contributes the stretching oI the pore wall in x-y
plane as shown in Eigure 37.
82
circles represent the change at high RH in x-y plane (SAXS).
As the RH is reduced the curvature oI the meniscus increases and the magnitude
oI the stress due to Laplace pressure begins to increase. When its magnitude is more than
that oI the stress due to surIace tension, the porewall begins to compress as shown in the
Eigure. This explains the variation in the strain direction during desorption beIore
capillary evaporation. This deIormation is represented in Eigure 38.
82
82
83
circles represent the change at RH beIore capillary condensation.
The equation 26 is a straight line equation with variables c
x
and ln(P/P
o
). The
modulus can be represented Irom the slope extracted Irom the strain vs ln(RH) plot oI
SAXS data (P/P
0
RH). This is the elastic modulus oI the material.
=
(2 - S )
(27)
R8.314 J/Kg/K
-1
; T294K; V18 x 10
-6
; v0.17, Slope c / ln(RH).
Apart Irom the estimation oI strain in x-y plane in SAXS, the strain Irom all
planes is estimated Irom the ESDP oI the WAXS, which is the primary objective oI this
83
x
and ln(P/P
o
). The
SAXS data (P/P
0
=
(2 - S )
(27)
R8.314 J/Kg/K
-1
; T294K; V18 x 10
-6
83
x
and ln(P/P
o
). The
SAXS data (P/P
0
=
(2 - S )
(27)
R8.314 J/Kg/K
-1
; T294K; V18 x 10
-6
84
study. The strain is estimated with ESDP peak position in the same way as the SAXS
and it is also plotted against the natural logarithm oI RH.
Figure 39. The strain calculated Irom ESDP vs the ln(RH) Ior MCM-41 AS`. The
trendline corresponds to the data points(black) beIore the capillary evaporation. The inset
shows the slope and the error in the trendline.
-2.5O -2.25 -2.OO -1.75 -1.5O -1.25 -1.OO -O.75 -O.5O -O.25 O.OO
-O.OO6
-O.OO5
-O.OO4
-O.OO3
-O.OO2
-O.OO1
O.OOO
S
t
r
a
i
n
_
W
A
X
S
ln(RH)
Equaticn y = a + b*x
W eight Nc W eighting
Residual Sum
cf Squares
5.31695E-7
Pearscn's r O.97963
Strain_W AXS lntercept 1.35433E-4 1.96682E-4
Strain_W AXS Slcpe O.OO559 4.O54O1E-4
85
Figure 40. The strain calculated Irom ESDP vs the ln(RH) Ior MCM-41 AN`. The
-2.5O -2.25 -2.OO -1.75 -1.5O -1.25 -1.OO -O.75 -O.5O -O.25 O.OO
-O.OO6
-O.OO5
-O.OO4
-O.OO3
-O.OO2
-O.OO1
O.OOO
S
t
r
a
i
n
_
W
A
X
S
ln(RH)
Equaticn
y = a + b*x
Weight Nc Weighting
Residual Sum
cf Squares
4.5218E-7
Pearscn's r O.97764
Adj. R-Square O.95O87
WAXS_Strain(p lntercept -O.OO227 1.42682E-4
WAXS_Strain(p Slcpe O.OO4O4 2.89617E-4
86
Figure 41. The strain calculated Irom ESDP vs the ln(RH) Ior SBA-15 AS`. The
-2.5O -2.25 -2.OO -1.75 -1.5O -1.25 -1.OO -O.75 -O.5O -O.25 O.OO
-O.OO3
-O.OO2
-O.OO1
O.OOO
O.OO1
O.OO2
S
t
r
a
i
n
_
W
A
X
S
ln(RH)
Equaticn
y = a + b*x
W eight Nc W eighting
Residual Sum
cf Squares
4.11OO6E-7
Pearscn's r O.88O91
Strain(p)
lntercept -1.62817E-4 4.14194E-4
Slcpe O.OO6O5 O.OO188
87
Figure 42. The strain calculated Irom ESDP vs the ln(RH) Ior SBA-15 AN`. The
The WAXS strain corresponds to the averaged variation oI distances between
atomic scales. The biggest contrast between the WAXS and SAXS strain is that the
Iormer is always compression i.e. negative strain. At high RH, the whole material is
under compression and reaches the highest compression with reducing RH. In MCM-41
the highest compression is reached at the RH in which the capillary evaporation begins.
In SBA-15 the highest compression is reached at a RH during the capillary evaporation.
-2.5O -2.25 -2.OO -1.75 -1.5O -1.25 -1.OO -O.75 -O.5O -O.25 O.OO
-O.OO4
-O.OO3
-O.OO2
-O.OO1
O.OOO
O.OO1
O.OO2
S
t
r
a
i
n
_
W
A
X
S
ln(RH)
Equaticn
y = a + b*x
Weight Nc Weighting
Residual Sum
cf Squares
3.25657E-7
Pearscn's r O.81946
Strain(p) lntercept -O.OO14 3.68689E-4
Strain(p) Slcpe O.OO414 O.OO167
88
Eurther decrease in RH relaxes the material gradually to the stress Iree conIiguration in
both samples.
The new technique developed in this study is extracting the strain Irom WAXS
by a similar approach as SAXS. The WAXS peak represents the whole solid silica
scaIIold in all planes. The strain calculated using the shiIt oI the peak as earlier will yield
the averaged strain on all planes. Using equation 14 and substituting the appropriate
stresses Irom table 2 we get,
= (2 - S ) + (28)
= (29)
The strain in the x-y planes have been discussed earlier in the SAXS method.
= (1 - 4 ) - (1 + 2 ) (Su)
The above equation represents the strain in the z direction due to the stresses. At
the highest RH the strain is negative, which implies that it is compressed in z plane. As
the RH decreases, the Iirst term becomes positive and eventually greater than the other
two terms. This consequently changes the direction oI the strain Irom compression to
tension. This change occurs aIter the capillary evaporation in MCM-41 and at the
beginning oI the capillary evaporation in SBA-15 samples. This argument is arrived by
plugging the constants in the equation 30 and setting c
z
to zero. (
LV
0.072 N/m; V18 x
10
-6
; v0.17; R8.314 J/Kg/k
-1-
; T294K; r
1
Irom the table 1 Ior each sample.
The average strain can be expressed as,
=
1
S
( + + ) (S1)
89
AIter substitutions,
=
S
(S - 1u ) +
S
(1 - 2 ) (S2)
The above equation is a straight line equation with variables c
x
and ln(P/P
o
). Now
the modulus can be represented Irom the slope extracted Irom the strain vs ln(RH) plot oI
WAXS data(P/P
0
RH). The modulus can be calculated using,
=
(S - 1u )
S
(SS)
R8.314 J/Kg/k
-1
; T294K; V18 x 10
-6
; v0.17, Slope c
avg
/ ln(RH).
The moduli E estimated by the two methods must represent the same quantity, as
it is measured Irom the same material. Hence the equation 27 and equation 33 can be
equated to estimate the Poisson`s ratio oI the material. Surprisingly, the poisson`s ratio
was Iound to be closer to the value oI a metal than the bulk silica(0.17). AIter the
estimation oI the Poisson`s ratio, it can be used to estimate the modulus oI the material
using equation 27. This is a very signiIicant advantage oI the novel technique oI
estimating the strain using the WAXS.
90
Table 3
The Poissons ratio estimated bv WAXS/SAXS
Sample Poisson`s ratio
MCM-41 AS` 0.30 + 0.02
MCM-41 AN` 0.27 + 0.02
SBA-15 AS` 0.33 + 0.1
SBA-15 AN` 0.33 + 0.12
Table 4
The modulus estimated bv SAXS method
Sample Modulus(GPa)
MCM-41 AS` 16.2 + 1.1
MCM-41 AN` 25.6 + 1.9
SBA-15 AS` 12.4 + 5.0
SBA-15 AN` 18.8 + 7.4
The elastic modulus oI the AS` is less than AN` oI each sample. In MCM-41,
according to the data Irom the gas-sorption method (table1) the pore width decreases with
annealing. The decrease in the pore width increases the curvature, which internal stress
built on the pore wall increases. The increase in internal stress will reduce the eIIective
strain due to the applied stress. Thus the elastic modulus oI the AN` sample is greater
than the AS`.
91
In SBA-15, the data Irom gas sorption shows that the pore width decreases with
the annealing. The greater elastic modulus oI the AN` sample is the result oI the increase
in pore width due to annealing. In both samples the modulus oI the annealed Iorm is
nearly 50 stronger which is very signiIicant then the diIIerence in the strength between
the materials. Thus it is inIerred that the internal stress plays a vital role in the strength oI
the material than the structure oI the pore.
The diIIerence between the MCM-41 and SBA-15 is due to the micropores. The
micropores in SBA-15 reduce the internal stress due to the absence oI the material. The
lesser internal stress oI SBA-15 decreases the elastic modulus oI SBA-15 than MCM-41.
Table 5
Compilation of the results obtained from Gas-sorption, SAXS and WAXS methods
Properties/Sample MCM41-AS` MCM41-AN` SBA-15 AS` SBA-15 AN`
Pore width (A) 26 24 60 59
Porewall thickness (A) 15 16 48 48
SurIace Area (m
2
/g) 1082.23 1132.88 367.9 368.44
Micropore Area (m
2
/g) 0 0 147.9 130.19
Poisson`s ratio 0.3 + 0.02 0.27+0.02 0.33+0.1 0.33+0.12
Modulus -SAXS (GPa) 16.2 + 1.1 25.6 + 1.9 12.4 + 5.0 18.8 + 7.4
The error analysis oI the SAXS and WAXS methods are given in Appendix A.
92
CHAPTER 6: CONCLUSION
In this study, a novel x-ray technique Ior the estimation oI the strain oI porous
silica by capillary condensation using WAXS was developed. The earlier techniques
using SAXS estimates the strain in the plane perpendicular to the pore channel. The
combination oI these two techniques will enable the estimation oI the Poisson`s ratio oI
the material which was unprecedented till now. The Poisson`s ratio oI MCM-41 and
SBA-41 were Iound to be closer to the value oI a metal than the value Ior silica. This is
the most interesting result oI this study and this result would oIIer more control over the
mechanical properties oI these materials in applications.
The Iorces acting on the porous structure due to the capillary action was studied
closely. AIter careIul contemplation the Iactors ignored in the previous methods have
been identiIied and the corrections were suggested Ior accurate results. It was Iound that
the modulus oI MCM-41 was greater than SBA-15 in both annealed` and as
synthesized` Iorms. The higher modulus oI MCM-41 seems to be due to the absence oI
micropores in it. The diIIerence in the modulus between these two nanoporous materials
was already known earlier by SAXS method but was reiterated here with the suggested
corrections. The annealed` Iorms have higher modulus than the as synthesized` Iorms,
due to the contraction oI pores during annealing process which increases the internal
stress. This diIIerence is more signiIicant, annealing make the materials nearly 50
stronger. This oIIers another dimension which can be controlled in synthesis to produce
materials with requisite mechanical properties.
93
The accuracy oI the new WAXS technique is highly related to the quality oI the
data. The obvious limitation oI this method is the existence oI ESDP Ior the scattering
pattern oI the examined nanoporous material. The new technique increases the range oI
the materials that can use x-ray scattering technique to estimate the strain as the WAXS
method does not require the ordered arrangement oI pores like the existing SAXS
method. The presence oI micropores in SBA-15 necessitates a better strategy oI analysis
oI its strain, which might reduce the error experienced in this study. This technique
provides more inIormation on the physical parameters oI porous silica than beIore.
94
REFERENCES
1
S.J. Gregg and K.S.W. Sing, Adsorption, SurIace Area and Porosity (2
nd
Ed., Academic Press,
1982).
2
C.H. Amberg, R. McIntosh, Can .J. Chem. 30, 1012 (1952).
3
C.T. Kresge, M. ELeonowicz, W.J. Roth, J.C. Vartuli, J.S. Beck, Nature 359, 710-712 (1992).
4
J.S.Beck, J.C. Vartuli, W.J. Roth, M.E. Leonowicz, C.T. Kresege, K.D. Schmitt, C.T. Chu, D.H.
Olson, E.W. Sheppard, S.B. McCullen, J.B. Higgins, J.L. Schlenker, J. Am.Chem.Soc. 114,
10834-10843 (1992).
5
D.Y.Zhao, J.L. Eeng, Q.S. Huo, N. Melosh, G.H. Eredrickson, B.E. Chmelka and G.D. Stucky,
Science 279, 548 (1998).
6
E.T. Meehan, Proc. R. Soc. London A 115, 199-207 (1927).
7
D.H. Bangham, N. Eakhoury, Nature 122, 681-682 (1928).
8
R.S. Haines, R. McIntosh, J. Chem. Phys. 15910, 28-38 (1947).
9
J.Prass, D. Muter, P. Eratzl and O. Paris, APL 95, 083121 (2009).
10
G.Y. Gor and A.V. Neimark Langmuir 26(16), 13021-13027 (2010).
11
S.Lowell, Joan E. Shields, Martin A. Thomas and Matthias Thommes, Characterization oI
Porous Solids and Powders: SurIace area, pore size and density (Springer, 2006).
12
C.Y. Chen, S.L. Burkett, H.X. Li, M.E. Davis, Microporous Mater. 2, 27-34 (1993).
13
O. Regev, Langmuir 12, 4940 -4944 (1996).
14
H.B.S.Chan, P.M. Budd, T.D. Naylor, J. Mater. Chem. 11, 951-957 (2001).
15
Z .Nan, M. Wang and B. Yan, J. Chem. Eng. Data 54, 83-89 (2009).
16
E. HoIImann, M. Cornelius, J. Morell, and M. Eroba, Silica-Based Mesoporous Organic
Inorganic Hybrid Materials.
95
17
K. Elodstro M, C. V. Teixeira, H. Amenitsch, V. AlIredsson and M. Linden Langmuir 20,
4885-4891 (2004).
18
S. Ruthstein, V. Erydman, S. Kababya, M. Landau and D. GoldIarb J. phys. Chem. B 107,
1739-1748 (2003).
19
D. Zhao, Q. Huo, J. Eeng, B. E. Chmelka and G. D. Stucky JACS 120, (24) 6024 (1998).
20
H. Kayser, Wied. Ann. 14, 451 (1881).
21
E. Eontana, Memorie Mat. Eis. Soc. Ital. Sci. I, 679 (1777).
22
N.T. de Saussure, Gilbert`s Ann. 47, 113 (1814).
23
E. Mitscherlich, Pogg. Ann. 59, 94 (1843).
24
I. Langmuir, J.Am. Chem. Soc. 40, 1631 (1918).
25
S. Brunauer, P.H. Emmet and E. Teller, J. Am. Chem. Soc. 60, 309 (1938).
26
G.P. Wilhite, WaterIlooding (SPE Textbook Series, Vol. 3, 1986).
27
URL:http://www.co-nan.eu/pdI/ij.pdI
28
P. A. Webb and C. Orr, Analytical Methods in Eine Particle Technology (Micromeritics, 1997).
29
Lorna J. Gibson and Michael Ashby, Cellular Solids-Structure and Properties (Cambridge,
1997).
30
M. Vable, Mechanics oI Materials (2002).
31
A. Grosman and C. Ortega, Phys. Rev. B 78, 0854333 (2008).
32
A. Marchand, J. H. Weijs, J. H. Scoeijer and B. Andreotti Am. J. Phy 79, 10, 999-1008 (2011)
33
S. Das, A. Marchand, B. Andreotti and J. H. Snoeijer, Elastic deIormation due to tangential
capillary Iorces, ArXiv 1103.0782 (2011), URL http://arxiv.org/abs/1103.0782.
34
G. Barnes & I. Gentle, InterIacial Science: An Introduction (OxIord Press, 2005).
35
URL:http://www.goiit.com/upload/2009/7/12/b77d9c924d82Ic73685e9596b85I65891.giI
36
J. Als-Nielsen, D. McMorrow, Elements oI Modern x-ray Physics (Wiley, 2011).
37
URL:http://www.micromeritics.com/
96
38
H. Schnablegger, Y.Singh, A Practical Guide to SAXS (Anton Paar, 2006).
39
L. Kirkup, Data Analysis with Excel (Cambridge, 2002).
97
APPENDIX A: ERROR ANALYSIS
The Iormula Ior calculating the modulus can be generalized Irom equation 27 and 33 as,
=
ln ( )
k` represents the constants in those equation. The slope extracted Irom the strain c vs
ln(RH) plot gives the modulus E. Those two Iactors are plotted with the assumption oI
negligible deviation (precision error) in the relative humidity (RH). The measured RH is
precise and it is varied constantly by 5 in the experiment. Hence the error in RH is
independent oI strain. The standard error in the slope oI a trendline always gives the error
oI the term in the y axis
39
. In this plot it is the strain c so its error (Ac) is the standard
error oI the slope. The accuracy error in RH due to the instrument error is 2. The 2
error is the deviation in each change oI 5 in the experiment.
The error in E is given by the root oI the sum oI the squares oI each error
39
. Hence the
error in the modulus (AE) becomes:
A =
A
+
A
ln ( )
98
APPENDIX B: KELVIN EQUATION
Figure. Spherical liquid-gas interIace in a capillary oI radius r
m
.
The Iigure represents a curved interIace between the vapor phase u and liquid phase ,
hence Laplace equation is expressed as,
= - = (1)
The chemical equilibrium with chemical potential can be expressed as,
= = (2)
Now iI the equilibrium is shiIted with small changes in p
o
, p
,r
m
and
i
, the expressions
become,
- = 2
1
(S)
= = (4)
98
m
.
= - = (1)
= = (2)
o
, p
,r
m
and
i
, the expressions
become,
- = 2
1
(S)
= = (4)
98
m
.
= - = (1)
= = (2)
o
, p
,r
m
and
i
, the expressions
become,
- = 2
1
(S)
= = (4)
99
By using the Iirst law oI thermodynamics and Maxwell`s relation at constant temperature,
constant volume V
o
, V
and constant number oI molecules in each phase, the equation 4

becomes,
= = (S)
Using equation 5 in equation 3 with the assumption that volume oI the gas phase V
is
greater than the volume oI the liquid phase V
o
,
2
1
= ( ) (6)
Integrating equation 6 Irom a Ilat surIace to curvature r
m
and using equation 4, we get
2
1
= - (7)
The vapor is assumed to be ideal gas, so
- = ln ( ) (8)
Using equation 8 in equation 7,
=
2
=
-
(9)
The terms p
o
and p
are replaced by the corresponding terms, the vapor pressure oI the

gas P
*
and the saturated vapor pressure oI the liquid P
o
. The volume oI the liquid V
o
is
replaced by molar volume V.
Erom the Iigure, r r
m
/ cos0,
=
2
=
-
(1u)
This is equation is known as Kelvin equation. This derivation was based on |reIs.34, 11|.

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