Coatings with inversely switching behavior [Elektronische Ressource] : new applications of core-shell hydrogel particles / von Horecha Marta

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Coatings with Inversely Switching Behavior. New Applications of CoreShell Hydrogel Particles. D I S S E R T A T I O N zzuurr EErrllaanngguunngg ddeess aakkaaddeemmiisscchheenn GGrraaddeess zzuurr EErrllaanngguunngg ddeess aakkaaddeemmiisscchheenn GGrraaddeess Doctor rerum naturalium ((((DDDDrrrr.... rrrreeeerrrr.... nnnnaaaatttt....)))) vorgelegt der Fakultät Mathematik und Naturwissenschaften der Technischen Universität Dresden von HORECHA MARTA ggggeeeebbbboooorrrreeeennnn aaaammmm 00004444 AAAAuuuugggguuuusssstttt 1111999977776666 iiiinnnn LLLLvvvviiiivvvv,,,, UUUUkkkkrrrraaaaiiiinnnneeee Eingereicht am 22.07.2010 Die Dissertation wurde in der Zeit von Oktober 2006 bis Juli 2010 im Institut für Polymer Forschung, Dresden angefertigt 1. INTRODUCTION...................................................... 1 1.1 PROLOGUE AND MOTIVATION ........................................ 1 1.2 GOAL OF THE WORK: CREATION OF SURFACES WITH INVERSELY SWITCHABLE WETTING BEHAVIOUR ..................... 5 1.3 OUTLINE ....................................................................... 9 2. THEORETICAL BACKGROUND AND LITERATURE OVERVIEW ................................................................... 10 2.1 WETTING PHENOMENA ................................................ 10 2.2 SWITCHING OF SURFACE PROPERTIES BY MEANS OF RESPONSIVE SUBSTANCES AT INTERFACE ............................ 20 2.

Informations

• Publié par: technische_universitat_dresden
• Publié le: 01 janvier 2010
• Nombre de lectures: 14
• Langue: English
• Poids de l'ouvrage: 7 Mo

Extrait

Coatings with Inversely Switching Behavior.

NewApplicationsof CoreShell Hydrogel Particles.

D I S S ERTATION

zur Erlangung des akademischen Grades

Doctor rerum naturalium

(Dr. rer. nat.)

vorgelegt

der Fakultät Mathematik und Naturwissenschaften

der Technischen Universität Dresden

von

H ORECHA M ARTA

geboren am 04 August 1976 in Lviv, Ukraine

Eingereicht am 22.07.2010

Die Dissertation wurde in der Zeit von Oktober 2006 bis Juli 2010 im Institut für Polymer Forschung, Dresden angefertigt

1.3

1.2

1.

4.1

4.2

4.

SHELL ................................................................................ 65

3.5

1.1

OF SURFACE WETTABILITY .................................................. 25

RESPONSIVE SUBSTANCES AT INTERFACE ............................ 20

3.2

3.3

3.

3.1

C ONCEPTS TO OBTAIN AN INVERSE SWITCHING EFFECT

O THER METHODS ......................................................... 53

E VALUATION OF PARAMETERS OF INVERSE SWITCHING . 54

2.2

2.3

2.1

E XPERIMENTAL TECHNIQUES .............................. 37

S CANNING E LECTRON M ICROSCOPY ............................ 43

D YNAMIC L IGHT S CATTERING ...................................... 46

A TOMIC F ORCE M ICROSCOPY ....................................... 37

MODIFICATION .................................................................... 29

S YNTHETIC APPROACHES TO OBTAIN THE CORE  SHELL

W ETTING PHENOMENA ................................................ 10

2.4

3.4

OVERVIEW ................................................................... 10

T HEORETICAL

O UTLINE ....................................................................... 9

P ROLOGUE AND M OTIVATION ........................................ 1

D ROP S HAPE A NALYSIS T ECHNIQUE (DSA) ................. 51

H YDROGELS AS A “ SMART ” FOR SURFACE MATERIAL

2.

STRUCTURES HAVING HYDROGEL CORE AND HYDROPHOBIC

R ESULTS AND DISCUSSIONS ................................ 54

I NTRODUCTION ...................................................... 1

BACKGROUND AND LITERATURE

S WITCHING OF SURFACE PROPERTIES BY MEANS OF

INVERSELY SWITCHABLE WETTING BEHAVIOUR ..................... 5

G OAL OF THE WORK :C REATION OF SURFACES WITH

4.2.1S UBSTRATE SELECTION AND CHARACTERIZATION .................68 4.2.2“O NE  POT ”  SYNTHETIC ROUTE TO CORE  SHELL PARTICLES VIA INVERSE SUSPENSION POLYMERIZATION ..............................................70 4.2.2.1Synthesis and characterization of shellforming polymeric surfactant ............................................................................73 4.2.2.2Selection of the monomer for the formation of inner part of coreshell particles ...................................................................75 4.2.2.3Synthesis of coreshell particles via inverse suspension polymerization and their characterization ......................78 4.2.2.4“Contraphilic” surfaces prepared using coreshell particles synthesized by “onepot” approach.......................................83 4.2.3P REPARATION OF THE CORE  SHELL PARTICLES VIA “ BOTTOM  UP ” APPROACH ............................................................................93 4.2.3.1Synthesis, characterization and tuning the composition of coreforming microgels with suitable swelling effect .95

4.2.3.2Formation of loose periodic arrays of microgels on the substrate ......................................................................................102 4.2.3.3Surface density as a function of swelling effect .........107 4.2.3.4Measurements of the maximal pressure developing upon the swelling of the microgels ....................................................108 4.2.3.5Chemical modification of hydrogel microparticles.....110 4.2.3.6.............................115Confined swelling of the microgels 4.2.3.7Adsorption of oppositely charged nanoparticles on the surface of microgels............................................................................124 4.2.3.8Graftingfrom polymerization of shell on the microgels surface................................................................................128 4.2.3.9Utilization of polyisoprene latex for PI shell formation ......................................................................................134

4.2.3.10Crosslinking of the shell ............................................142

4.2.4S WITCHING PROPERTIES OF HYDROPHILIC SURFACES COVERED WITH HYDROPHOBIC CORE  SHELL MICROGELS SWELLABLE IN WATER  .......................................................................................... 146 4.2.4.1Responsive surfaces fabricated via “bottomup” approach: insitu AFM monitoring of the waterinduced change of

the surface coverage........................................................................... 146 5.S UMMARY .......................................................... 153

6.

R EFERENCES ..................................................... 159

PVA   poly(vinyl alcohol)

SEM  Scanning Electron Microscopy TGA  Thermogravimetric Analysis

temperature

PDI  polydispersity index PE  polyethylene

hydrochloride

SEC  Size Exclusion

tBA  tertbutylacrylate VA  vinylamine

BP  4hydrohybenzophenone

AIBN  azobis(isobutyronitril)

WCA  water contact angle

MAA  methacrylic acid

RMS  root mean square

NaHSS  N hydroxysulfosuccinimide

methacrylate)

TMP  trimethylpentane

MBA  N,N methylenbisacrylamide

DSA  Drop Shape Analysis

EDC  1ethyl3[3dimethyl

L IST OFABBREVIATIONS

aminopropyl] carbodiimide

PAA  poly(acrylic acid)

PDEA  poly(2(diethylamino)ethyl

NIPAM  N isopropylacrylamide

SAM  selfassembled monolayer

DMF  N,N dimethylformamide

NMR  Nuclear Magnetic Resonance

HLB  hydrophiliclipophilic balance KPS  potassium persulfate

AA  acrylic acid

PS  polystyrene

PMMA  poly(methyl methacrylate)

PI  polyisoprene

PAAm  polyacrylamide

PBPA  poly(benzophenone acrylate)

PEG  poly(ethylene glycol)

Chromatography

AFM  Atomic Force Microscopy

AAm  acrylamide

AEMA  2aminoehyl methacrylate

GPC  Gel Permission

VPT  volume phase transition

SDS  sodium dodecylsulfate

P4VP  poly(4vinylpyridine)

Chromatography

NBA  4Nitrobenzaldehyde

BPA  4acryloyloxybenzophenone DAIB  (diacetoxy) iodobenzene DCC  N , N 'dicyclohexylcarbodiimid DLS  Dynamic Light Scattering DMAP  4(dimethylamino)pyridin

PEO  poly(ethylene oxide)

PNIPAM – poly( N isopropylacrylamide)

PGMA  poly(glycidyl methacrylate)

PTFE  polytetrafluoroethylene

HEMA  2hydrohyethyl methacrylate

LCST  low critical solution

1.I NTRODUCTION

1 Introduction and Motivation

1.1P ROLOGUE AND M OTIVATION

Surface wettability has been a topic of scientific investigation for

over 60 years. This great level of interest has been fueled by the

fundamental

importance

of

wetting

phenomena

in

various

technological applications, e.g. textile technology, production of water

[1] [2] repellant materials , spraying of paints and agricultural chemicals ,

penetration of ink in paper, impart to fabrics adsorbing and desorbing

[3] properties , etc. Hydrophobic and superhydrophobic materials are

widely used for many functions including the design and manufacture

[4] [5] of selfcleaning panes , waterproof textiles, microfluidic devices ,

hydroprotection

[6] protection ,

of

reinforced

biofouling

concrete

[7] protection ,

constructions,

prevention

of

corrosion

capillary

condensation and icing, shielding of surfaces against radioactive,

organic, and inorganic contaminations and many others.

With such a high degree of applications in modern technologies,

the materials used are themselves the subject of modification with the

purpose of controlling their surface properties. It is noteworthy to

mention that the cost of materials being modified is an extremely

important factor for the evaluation of their innovative potential.

Usually, high costs of raw materials are the main limiting factor,

which restrict manufacture of the final product with desired technical

properties. Fortunately, wettability is a surface feature, which is

mainly defined by the structure and properties of a few nanometers

thick superficial layer rather than by the characteristics of the bulk

material as a whole. Therefore, one of the most productive and cost

efficient methods for the creation of novel materials is to develop an

1

1 Introduction and Motivation

external coating on the surface of existing ones. substances with dissimilar properties are usually used as coatings in order to correct or

totally change the surface properties of the raw material.

As a practical aspect of a material usage is often defined by its physical and chemical surface properties, numerous tasks could not be realized without the use of surface modifications, coatings and thin

film technology. Coating techniques can be used to improve a material technical feature, look and performance. Routinely used examples of such materials applications include wearresistant coatings, which are

used on tools or machine parts, or thin films on paned glass which optimize the transmission or reflection of selected parts of the

electromagnetic spectrum. Many innovative products would not even

exist without the special properties provided by thin films. Prominent examples are computer hard disc drive, optical data storage media like CDs, DVDs and Blueray disks, flat displays and thinfilm solar cells.

Therefore, the need for efficient and effective methods of surface modification becomes increasingly important in allowing the production of far superior products in terms of altered mechanical

(wear, friction resistance,) chemical (corrosion protection, permeation control, enhanced biocompatibility, thermal insulation), electrical (improved conductivity) or optical (transmission, reflection, absorption,

colour adjustment) properties. Coatings can provide complex functionalities to surfaces, significantly changing their properties, compared to uncoated material. Many coating deposition techniques and surface treatments are

available for this purpose. If secondary material is added to the surface, the process is referred to as coating deposition process; however, if the surface microstructure and / or chemical composition

are altered, then the process is referred to as a surface modification process. Selection of the coating deposition or surface modification techniques depends on the functional requirements, shape, size and

2

adapt their structure by the rearrangement of interfacial components

[10] devices ,

textiles,

Since the wetting behaviour of material is strongly dependent on

colloidal

principle.

properties from hydrophilic to hydrophobic and vice versa, are of

energy. A number of switchable or adaptive coatings, which react to

considerable interest because of their potential applications including

valves.

In

tissue engineering and cell growth, creation of “intelligent” breath

Surfaces with switchable wetting behaviour, able to change their

3

[8] and surfaces is required for new concepts of sensors , drug delivery

and

selfregulating

particular, the design of a new generation of such “smart” materials

assembly

under the changing of environment in order to minimize surface

active

different stimuli from the environment, can be created using this

resistance, wear and scratch resistance, chemical stability of a raw

properties of the substrate,

and

dynamically active systems, usually achieved by a combination of

the surface structure and chemical composition, it is possible to

of

prepare the surface as a dynamic system that consists of two

coating

improve adhesion, wettability, corrosion

the

correct reflection or modify optical properties, etc.

materials, they can also provide conductive properties to a surface,

compatibility, adhesion, coating equipment and cost.

Functional coatings can

microfluidic

modern coatings quality have turned to an idea of creation of adaptive

material,

[11] techniques .

[9] systems ,

Recently, the process of development and the improvement of

materials with opposite properties, such sensitive surfaces are able to

or sensitive (also called “smart” or “intelligent”) surfaces. Based on

waterrepelling

nature

Coatings applied by deposition techniques are basically of two

1 Introduction and Motivation

in the automotive, home appliances, hardware, costume, jewellery etc.

types  decorative and functional. Decorative coatings are widely used