Polymer, metal, and ceramic microtubes by strain-driven self-rolling [Elektronische Ressource] / vorgelegt von Kamlesh Kumar

Kamlesh

Description

Polymer, Metal, and Ceramic Microtubes by Strain-driven Self-rolling D I S S E R T A T I O N zur Erlangung des akademischen Grades Doktor rerum naturalium (Dr. rer. nat.) vorgelegt am Fachbereich Chemie der Fakultät Mathematik und Naturwissenschaften der Technischen Universität Dresden von Kamlesh Kumar geboren am 19 Juli 1980 in Jaipur, Indien Gutachter: Prof. Dr. M. Stamm Prof. Dr. H.-J. P. Adler Eingereicht am: Tag der Verteidigung: Dedicated To My Family IIAcknowledgement The completion of this thesis would not have been possible without the support, hard work and endless efforts of a large number of people. I wonder if I can convey my heartfelt appreciation and gratitude in any way possible to all people who are connected direct or indirect to this thesis. I am deeply indebted to Prof. Dr. Manfred Stamm for providing me an opportunity to carry out this work in IPF, and whose guidance, advice, constant motivation and encouragement, helped me in all the time of research and writing of this thesis. The efforts and help he extended made me to feel at home. I thank my advisor Dr. Valeriy Luchnikov for his valuable guidance and help during this thesis work. His wide knowledge and constant encouragement provided a good basis for my dissertation. I am also grateful to Dr.

Sujets

• Physik

Informations

• Publié par: technische_universitat_dresden
• Publié le: 01 janvier 2009
• Nombre de lectures: 33
• Langue: English
• Poids de l'ouvrage: 4 Mo

Extrait

Gutachter: Prof. Dr. M. Stamm

geboren am 19 Juli 1980 in Jaipur, Indien

von

(Dr. rer. nat.)

Self-rolling

Polymer, Metal, and Ceramic Microtubes by Strain-driven

D I S S E R T A T I O N

zur Erlangung des akademischen Grades

der Fakultät Mathematik und Naturwissenschaften

Eingereicht am:

 Prof. Dr. H.-J. P. Adler

Tag der Verteidigung:

am Fachbereich Chemie

Doktor rerum naturalium

der Technischen Universität Dresden

Kamlesh Kumar

vorgelegt

Dedicated To My Family

II

Acknowledgement

The completion of this thesis would not have been possible without the support, hard work

and endless efforts of a large number of people. I wonder if I can convey my heartfelt

appreciation and gratitude in any way possible to all people who are connected direct or

indirect to this thesis.

I am deeply indebted to Prof. Dr. Manfred Stamm for providing me an opportunity to

carry out this work in IPF, and whose guidance, advice, constant motivation and

encouragement, helped me in all the time of research and writing of this thesis. The efforts

and help he extended made me to feel at home.

I thank my advisor Dr. Valeriy Luchnikov for his valuable guidance and help during this

thesis work. His wide knowledge and constant encouragement provided a good basis for my

dissertation. I am also grateful to Dr. Bhanu Nandan for the help and support which I received

from him during my stay in Dresden. The way both helped me to complete my thesis is

wonderful and it is not easy to express in words.

I gratefully acknowledge Dr. Frank Simon and Dr. Petr Formanek, respectively for their

help in XPS, SEM measurement; Dr. Martin Müller and Gudrun Adam for FTIR

measurements. I thank Mrs. P. Scheppan and Dr. U. Burkhardt from Max Planck Institute for

Chemical Physics of Solid, Dresden for their help in EDX analysis. I also thank Dr. Jens

Ingolf Mönch from Leibniz Institute for Solid State and Materials Research Dresden (IFW)

for deposition of gold patterns.

I would like to specially thank Prof. I. K. Varma for her tacit knowledge and moral

support in very difficult times. Furthermore I would like to express my gratitude to Dr. V.  III

Senkovskyy for the synthesis of poly(4-bromostyrene) and Dr. A. Kiriy and Dr. E. Bhoje

Gowd for their nice suggestions during my work. I also thank to my colleagues Mukesh

Kumar Vyas, Prashant Sinha, Fabio Crobu, Smrati Gupta, Eva Herold, Marko Kuntzsch,

Konstantin Demidenok, Vera Bocharova, Martha Horchea and Sina Burket for their

cooperation and support in my work.

I would also like to thank my friends Bitu, Stefan, Prashant Menezes, Sameer,

Pradyumn, Dipti, Alok, Vishal, Vikram, Manoj, Saurabh, Satpal, Biplap, Sunil and Deepa.

Without their help would have been difficult to live so far away from family and to complete

thesis.

To my family, I thank them for always being there for me and for giving me

unconditional support and love. Words are inadequate to thank my parents, brother, and

sisters, whose inspiration, understanding, patience and support have always been a source of

encouragement in carrying out the work. I would like to specially thank Satish, Mahesh,

Mukesh, Shimbu, Neelu, Reenu, and Meenu for accommodating my work and encouraging

me to strive for more at each step.

This research work was made possible by the financial support from IPF Dresden.

IV

Abstract A thin polymer bilayer film was transformed into micro- and nano-tubes using strain driven

self-rolling phenomena of polystyrene (PS)/poly (4-vinyl pyridine) (P4VP) film. Polymer

bilayer was produced by consecutive deposition of PS and P4VP, from toluene and

chloroform solutions, respectively, by dip-coating technique. The object formation proceeds

from a opening in the film made by photolithography or by mechanical scratching followed

by immersion of patterned sample in dodecylbenzene sulfonic acid (DBSA) solution. DBSA

forms supramolecular complexes with pyridine rings of P4VP and increases the specific

volume of the polymer. Since the solution is neutral to PS layer, bilayer film develops strain

due to unequal swelling of polymers in solution of DBSA and hence the film bends and

scrolls in order to minimize its free energy and form tubes. The length of the tubes and the

direction of rolling are determined by mechanical patterning of the film. UV-photolithography

is used to fabricate patterns of polymer bilayer in order to create tube in a precise manner. The

kinetics of the tube formation was studied with respect to acidity of the solution and UV dose.

Rate of rolling increased with the acidity of the solution. Tube diameter and rate of rolling

decreased with the increase of the UV exposure time. Films with 2-dimensional gradients of

layer thicknesses were prepared to study a broad range of parameters in a single experiment.

Furthermore, polymer micro-toroids and triangles were also fabricated using self-rolling

approach of PS/P4VP layer. Moreover, the kinetics of toroid formation is also studied in the

present work. The equilibrium dimensions of toroid are determined by the balance of the

bending and the stretching energies of the film. The width of the rolled-up bilayer is larger for

the films with higher values of the bending modulus and smaller values of the effective

stretching modulus.

Moreover, self-rolling phenomena of polymer layer was also explored as a template to

fabricate metal, ceramic and metal/ceramic hybrid tube. In order to fabricate metallic and

V

bimetallic tube, the cross-linked polymer film is capped by metallic layer. After rolling,

polymer template is removed by pyrolysis resulting in pure metal microtubes. The fabrication

of silica and silica/gold hybrid tubes of high

aspect ratio is also demonstrated.

Polydimethylsiloxane (PDMS) is used as a precursor of the silica and it is converted into

silica by pyrolysis at high temperature. Entire polymer moiety is also removed at this

temperature. In order to fabricate hybrid tube of silica with gold, a thin gold layer is deposited

on the polymer layer by physical vapour deposition.

Self-rolling of polymer bilayers is a very convenient approach for interfacing the

interior of microtubes with external electrical circuits and it can be used in particular for

creating devices as micro-bubble generators exploiting electrolytic decomposition of fluids. A

demonstration of microbubble generation inside the polymer tube is shown in this work.

Possibility to functionalize the hidden walls of the tubes is one of the major advantages

of the self-rolling approach. One can modify the surface of the film prior to rolling by

magnetron sputtering of metal and upon rolling, tube and toroids with metallized inner surface

could be obtained. The tube and toroids with metallic inner surface are promising for the

future research as IR-frequency range resonators. Polymer and metallic microtubes fabricated

by self-rolling

approach may find

applications in such fields as

IR-waveguiding,

microfluidics, enzyme bi-reaction, chemical and biochemical sensing. The silica and

silica/gold

hybrid tubes have potential use in optoelectronic devices and in catalytic

applications.

VI

Chapter 1: Introduction

TABLE OF CONTENTS

 1.1 Preface and Motivation  1.2 Goal  1.3 Outline Chapter 2: Mechanism of strain-driven self rolling in thin multi-layer films

2.1Theoretical background 2.2 Self-rolling of semiconductor thin films 2.3 Swelling behaviour of polymers, networks and super absorbers 2.4 Self-rolling of polymer bilayer films Chapter 3: Experimental

1 4 5

8 12 14 17

3.1 Materials 21 3.2 Characterization techniques 3.2.1 Null ellipsometry 22 3.2.2 Optical microscopy 24 3.2.3 Fluorescence microscopy 25 3.2.4 Scanning electron microscopy 27 3.2.5 Atomic force microscopy 29 3.2.6 Infrared spectroscopy 30 3.2.7 X-ray photoelectron spectroscopy 33 3.2.8 Energy dispersive X-ray Analysis 35 Chapter 4: Formation of Self-rolled Polymer Microtubes Studied by Combinatorial

Approach

4.1Introduction 4.2Fabrication of tube 4.3Results and discussion 4.3.1Parameters affecting the diameter of tube a)Effect of the thickness of the polymer layer on the tube’s dimensions b)Effect of UV exposure dose on tube diameter

VII

39 41 42 45 46 49

c)Rate of rolling (i) The effect of UV irradiation doses on the rate of tube rolling (ii) The effect of concentration of the acidic solution on the rolling rate d) Effect of acid concentration on tube diameter 4.3.2 Fluid transport in rolled-up polymer tube 4.4 Discussion 4.5 Conclusions Chapter 5: Fabrication of polymer microtoroids

5.1Introduction 5.2Experimental 5.3Results and discussions 5.4Kinetics of micro-toroids formation 5.5Model for the micro-toroids formation 5.6Discussion 5.7Conclusions Chapter 6: Formation of metallic/bimetallic microtubes

6.1Introduction 6.2Experimental 6.3Results and Discussions 6.4Kinetics of tube formation 6.5Conclusions Chapter 7: Fabrication of silica and metal/silica hybrid tubes

7.1Introduction 7.2Experimental 7.3Results and discussion 7.4Discussion 7.5Conclusions

VIII

50 51 51 52 53 57 59

61 62 64 66 67 70 71

74 75 75 85 91

93 94 95 104 105

Chapter 8: Bubble generation inside the tube

8.1Introduction 8.2Fabrication of bubble generation device 8.3Results and discussions 8.4Discussion 8.5Conclusions Chapter 9: Summary and outlook

References

Appendixes

IX

108 110 112 120 121

123

130

146

Chapter 1

1.1 Preface and Motivation

1. Introduction

The formation of tubular structures of micron and sub-micron dimensions is an emerging

area because of potential applications of these objects in various fields such as micro and

nanofludic systems [Thu06, Teg04], wave-guide [Kip06], electronics [Tak08] and nanojet

printing [Voi01]. Mesoscopic dimensions of the tubular-based devices allow for precise control

over the tiny amounts of gas, chemicals and solvents, and permit to manipulate with the

thermodynamical parameters of the system (temperature, pressure) with high rate and precision

[Squ05, Ho98, Lel04, Het05, Mal99]. Moreover, the behaviour of fluids geometrically

constrained to small, micron and sub-micron natural or artificial compartments is known to

differ considerably from the bulk characteristics [Guo06]. Miniaturisation and reduction of the

energy requirements of these systems are additional advantages of these systems.

There exist numerous approaches to the production of micro- and nanoscale tubular

structures. The template based [Mar94] and template free [Hop04] methods are widely used to

fabricate tubes of polymers, semiconductors, metals and other materials on a micro and

nanoscopic scale. Typically, a membrane which contains nanopores of uniform diameter is

used in a template method. With the help of porous membrane monodisperse nanocylinders of

the desired material, whose dimensions can be carefully controlled, are obtained. Polymer,

metal and hybrid nano- and mesotubes can also be synthesized by coating on degradable

polymer template fibers [Bog00]. Extremely thin degradable polymer fiber templates are first

coated with the desired wall materials and later subjected to selective removal of the core

material forms the tubes.

Although the template methods of the mesotube’s fabrication are simple, cheap and

permit high output, however, they allow only reduced control over the functionalization of the