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PROPERTIES OF HYDROGELS
Ting Yang
AKADEMISK AVHANDLING
Som med tillstnd av Kungliga Tekniska hgskolan i Stockholm, framlgges till offentlig
granskning fr avlggande av teknisk doktorsexamen torsdag 6 december 2012, kl. 10:00 i
sal F3, Lindstedtsvgen 26, KTH, Stockholm. Avhandlingen frsvaras p engelska.
Fakultetsopponent: Professor Jns Hilborn frn Uppsala University, Sweden
Copyright 2012 Ting Yang
In the main part of this work, bi-functional poly(ethylene glycol) (PEG) precursors with
either thiols (PEG-SH) or allyls (PEG-Al) , covering molecular weights from 3 kDa to 8
kDa were synthesized and thoroughly characterized by 1H NMR, 13C NMR, FT-Raman
and MALDI-TOF techniques. By combining PEG precursors with complementary
trifunctional crosslinkers, a library of well-defined single-network hydrogels was
efficiently constructed via the robust UV-initiated thiol-ene coupling (TEC) chemistry.
Novel sequential interpenetrating network (seqIPN) hydrogels based on PEG were
fabricated by diffusing and afterwards crosslinking secondary-network precursors within
dense (2 kDa) to loose (8 kDa) primary networks. The impacts of polymer chain length
and diffusion time on the swelling and mechanical properties were assessed for the seqIPN
hydrogels. Additionally, disperse red 13 decorated PEG 2 kDa and 8 kDa were synthesized
and used as probes to monitor the secondary-network precursor diffusion rate by UV/Vis
spectroscopy.
FT-Raman and leaching tests were conducted to evaluate the efficiency of the TEC
reaction for the development of PEG networks and their gel fractions. All gels were fully
crosslinked within 5 minutes and with the gel fraction above 84%. The chain length of
PEG, location of functional groups of PEGs, solvents, solid content were found to have
directly influence on the mechanical and swelling properties of PEG single-network
hydrogels. The utilization of the diffusion time dependent seqIPN strategy enabled further
freedom to control the swelling and mechanical properties of PEG hydrogels, with the
degree of water swelling ranged from 280 870% and the tensile modulus ranging from
1135 kPa to 175 kPa.
Furthermore, the seqIPN strategy was utilized for fiber reinforced free radical polymerized
hydrogels. N, N-dimethylacrylamide (DMA) with crosslinker poly(ethylene glycol)
diacrylate were diffused in bacterial cellulose (BC) aerogel thereafter UV crosslinked to
form BC-DMA hydrogels. FT-Raman and leaching tests were conducted to evaluate the
efficiency of the free radical polymerization and the BC-DMA gel fractions. After UV cure
for 10 minutes, robust DMA networks were formed within BC aerogels with over 94% gel
fraction. The high porosity and robust interpenetrating DMA network within BC fibers
were further analysed with FE-SEM. Compression tests showed that fiber reinforced DMA
hydrogels have higher compression modulus than DMA hydrogels, ranging from 4.4 to 8.3
MPa with water content from 78 to 70%.
SAMMANFATTNING
Under de senaste decennierna har hydrogeler studerats som nytt mjukt material och ven
tillmpats i biomedicinska applikationer ssom produktion av lkemedel och inom
vvnadsteknik.
I detta arbete har bifunktionell poly(etylenglykol) (PEG) med antingen tioler (PEG-SH 3
kDa till 8 kDa) eller allyler (PEG-Al 3 kDa) syntetiserats och karakteriserats med hjlp av
tekniker ssom 1H-NMR, 13C-NMR, FT-Raman samt MALDI-TOF. Kompletterande
trifunktionella tvrbindare anvndes fr att tvrbinda dessa bifunktionella PEG-system till
vldefinierade ntverk (hydrogeler) med hjlp av robust UV-initierad tiol-en kemi (TEC).
Av PEG-Al-systemet (2 kDa till 8 kDa) tillverkades ven sekventiella interpenetrerande
ntverk (seqIPN), dr monomanerna till det sekundra ntverket fick diffundera in i ett
tidigare tvrbundet ntverk, varp det sekundra ntverket ocks tvrbands. Pverkan av
diffusionstiden hos det sekundra ntverket p seqIPN hydrogelernas egenskaper
utvrderades. Vidare utnyttjades disperse red 13-funktionaliserad PEG 2 kDa och 8 kDa
(PEG-rd) fr att utvrdera diffusionshastigheten hos det sekundra ntverket med hjlp av
UV/Vis spektroskopi. Mtningar visade att diffusionshastigheten pverkades av ttheten
hos det primra ntverket, med en lgre diffusionshastighet fr ttare tvrbundna ntverk.
Hydrogels as novel soft material have been studied for bio-application for over fifty years.
The good biocompatibility of hydrogels emanates from their higher water content (over
70%), but it is also a limitation to the mechanical properties so as the applications. Hereby,
establishing a database relating initial materials, fabrication factors and methods to
swelling and mechanical properties of hydrogels has been the main purpose of this study.
Preparing and assessing well-defined novel hydrogels have been the main part of the study
in which thiol and allyl bi-functionalized poly(ethylene glycol) (PEG) (Mn = 3 kDa to 8k
Da) were used to form hydrogels with the complementary trifunctional crosslinkers via
UV-initiated thiol-ene coupling chemistry. To improve while control the mechanical
properties of PEG hydrogels, sequential interpenetrating networks (seqIPN) were
introduced by diffusing secondary PEG network into dense (2k Da) to loose (8k Da)
crosslinked single networks. To further assess the properties of seqIPN, the influence of
secondary-network diffusion time in dense (2k Da) and loose (8k Da) network hydrogels
was studied. Swelling and tensile tests were conducted to evaluate the swelling and
mechanical properties of PEG hydrogels. Furthermore, PEGs decorated with disperse red
13 were used to investigate the diffusion rate by UV/Vis spectroscopy.
1
Introduction
2 INTRODUCTION
2.1 HYDROGELS
2
Introduction
Thiol-ene coupling (TEC) chemistry is an organic reaction between a thiol and an alkene
(Figure 2), which was discovered in 1905.5 The advantages of TEC are high efficiency,
high yielding in the presence of oxygen, tolerance of various solvents and functional
groups.5 In recent years, researchers have considered the TEC reaction to be a "click"
reaction.6 This reaction has been extensively applied in coating,7 nano-printing,8 adhesive
technology9 and in dendrimer chemistry or other well-defined structure syntheses.10 The
TEC addition reaction is typically facilitated by UV irradiation and proceeds through a
thiyl radical species. When TEC utilized in polymer chemistry, the polymerization follows
a free radical, step-growth mechanism.11
Figure 2. Scheme of thiol-ene coupling reaction. R and R contains thiol and allyl groups
respectively.
3
Introduction
allyl and methacrylate groups, which were used for TEC hydrogels preparation in this
work.
Figure 3. Poly(ethylene glycol) (PEG) and thiol, allyl, methacrylate functionalized PEG.
4
Introduction
In the main parts of this work, telechelic polymers based on PEG were used to fabricate
TEC networks. The molecular weight between crosslinks (Mc) is the number average
molecular weight between the crosslinking junctions and is a key component correlated to
diffusion properties of a network.26 The length in between the crosslinking junctions is
mesh size ().27 Figure 5 (a) illustrates an ideal network formed by bi-functional PEG and
complementary tri-functional crosslinkers via TEC, mesh size () or Mc of this network is
controlled by the polymer chain length.
5
Introduction
Figure 5. (a) TEC network formed by tri-functional crosslinker and bi-functional polymer.
(b) FRP network formed by monomers and bi-functional crosslinker.
Another hydrogel network used in this thesis is FRP network, which is formed by
monomers and bi-functional crosslinkers. Figure 5 (b) illustrates the FRP network that has
a random mesh size or Mc because of the different reactivity between the monomer homo-
polymerization and the monomer and crosslinker copolymerization; besides, the
polymerization can be terminated by different termination mechanisms.28
6
Introduction
network without crosslinking.39,40 Figure 6 shows full seqIPN formation, by TEC and FRP,
use UV curing and semiIPN formation use linear polymer. In all cases the components of
the secondary network are diffused into the primary network.
Figure 6. Full IPN and Semi IPN formation via sequential diffusion process.
Bacterial cellulose (BC) hydrogel is one of the most common natural cellulose which is
produced by acetic bacterium "Acetobacter xylinum".41,42 BC was first discovered in
1886,43-45 it has been intensively studied since 1947 and has ever since attracted scientists
attention.46 Although cellulose is insoluble in water and most organic solvents,47 the long
and refined nanoscale fibers of BC can form a physically entangled network and contains
around 98% water.48 Different from polymeric hydrogels, the hydrogen bonding between
water molecules and BC are mostly on the fiber surface, large amounts of free water are
filling the voids in between BC fibers, so the water in a cellulose hydrogel can be squeezed
7
Introduction
out easily. The advantages of BC hydrogel are not only green and sustainable49 with high
average molecular weight and crystallinity,50 but also are high dimensional stability after
converting the BC hydrogel into the respective aerogels.51,52 Figure 7 (a) and (b) is a
photograph of the raw BC hydrogels and the freeze-dried BC aerogels respectively. Figure
8 (c) demonstrates the FE-SEM picture of a BC network. Figure 7 (d) illustrates a scheme
of the hierarchical structure of a BC cellulose fiber, from the basic glucose chain to the
crystalline micro fibril and cellulose fiber.53,54
Figure 7. (a) Raw BC hydrogels, (b) freeze-dried BC aerogel, (c) FE-SEM picture of cross
section from BC aerogel, (d) scheme of BC fibrils structure: glucose chains, micro fibrils,
and cellulose fibers.
8
Introduction
Cellulose whiskers have been used as reinforcement to improve the mechanical properties
of hydrogels.55,56 Different from the cellulose whiskers, BC aerogel with the long fiber and
large voids in between the fibers is a suitable scaffold to improve the mechanical
properties of the brittle FRP hydrogels.
A crosslinked polymer hydrogels swell but not dissolve when water or a solvent enters it.
The swelling properties, which usually use degree of swelling to define hydrogels, depend
on many factors such as network density, solvent nature, polymer solvent interaction
parameter.1 The properties of water swelling of PEG hydrogels and PEG diffusion in PEG
networks were studied in this work.
Because water acts as a plasticizer in a hydrophilic polymer network system, the swelling
process of the hydrogel can be considered under rubbery state and can be described by the
free energy of mixing Gmix from the polymer and solvent interaction and the elastic free
energy Gelastic from the crosslinked network:57
At the beginning of swelling, the Gmix << 0, Gelastic > 0, Gmix + Gelastic < 0, so the
swelling is favoured and the solvent diffuses into the network. During the processing of
swelling, the Gmix and Gelastic both increased until Gmix =Gelastic and Gsystem =
Gmix + Gelastic = 0, so that the driving force for swelling is gone: equilibrium swelling is
reached and swelling stops.
9
Introduction
Mechanical tests were conducted to assess the hydrogel properties. To establish a library of
mechanical properties of hydrogels is to gather the information of the hydrogel network
and to determine the range of application. 58
Tensile properties were the mainly studied mechanical properties of PEG based hydrogels
in this work. Figure 8 displays a photo of a hydrogel sample in a tensile testing machine.
The hydrogel samples are cut into a dumbbell shape prior to assessment.
The compression and rheology properties were used to assess the mechanical properties of
fiber-reinforced hydrogels in this work. Rheology is the study of the flow of matter,
measurements being prepared by shearing the sample, as shown in Figure 9.
10
Introduction
2.5 APPLICATIONS
The hydrogels prepared in this work covered a large range of mechanical properties, from
a soft hydrogel such as PEG to a hard hydrogel such as BC-DMA. Because of the high
water content and biocompatibility of hydrogels, many applications are related to
biomedical usage.59,60
11
Introduction
Figure 10. Diagram of a drug-delivery system uses a biodegradable PEG hydrogel carrying
drugs and releasing at certain location.
12
Experimental
3 EXPERIMENTAL
3.1 MATERIALS
13
Experimental
3.2 INSTRUMENTATION
Nuclear Magnetic Resonance (NMR) spectra were recorded with a Bruker Avance
400 MHz instrument using CDCl3 as solvent. The solvent signal was used as
internal standard.
14
Experimental
To study the formation of the hydrogels using TEC chemistry, PEGs were
functionalized with thiol (PEG-SH) and allyl (PEG-Al) to prepared TEC hydrogels
with the complementary tri-functional triazine based crosslinkers. All the hydrogels
were prepared in 3 to 6 replicas with a thiol to allyl molar ratio set to 1:1 with 3
wt% initiator (Irgacure 651). Solvents and solid content were varied to study the
efficient of TEC in different reaction conditions. Figure 11 presents the scheme of
PEG hydrogels fabrication; Table 1 details the sample codes for the single network
hydrogels.
15
Experimental
16
Experimental
17
Experimental
Four molecular weights PEGs (2 kDa, 3 kDa, 6 kDa and 8 kDa), equimolar ratio
(1:1) with crosslinker TMP-tris-thiol and Irgacure 651 (3 wt%) were dissolve in
ethanol (EtOH) (50 wt% solid content) respectively to prepare single-network
hydrogels. Using TMP based crosslinker TMP-tris-thiol instead of triazine based
crosslinker was because the better solubility in EtOH for the hydrogel preparation
process. Each mixture was vortexed to homogeneous and poured into a Teflon mold
(thickness: 0.10 cm, width: 1.0 cm) and was covered with a glass slide to prevent
EtOH evaporation. The mixture solution was allowed to gel for 5 minutes under UV
exposure (365 nm, 28.5 mW/cm intensity, Blak-Ray xx-15BlB UV bench lamp) at
room temperature. A small part of the cured hydrogel was cut and dried overnight
for gel fraction tests. The rest of the hydrogels were immersed in deionized water
for 5 hours and immersed in ethanol (100%) for 3 hours to remove residues. The
cleaned hydrogels were dried in air overnight and then placed in a vacuum oven at
40 C for 1 hour. The single-network hydrogel sample code is S2 prepared from
PEG-Al, Mn = 2 kDa (PEG-Al-2k); hydrogel S3 prepared from PEG-Al, Mn = 3
kDa; hydrogel S6 prepared from PEG-Al, Mn = 6 kDa; and hydrogel S8 prepared
from PEG-Al, Mn = 8 kDa, all hydrogels were prepare in 6 to 10 replicas, the S8
hydrogels were prepared in at least 12 replicas.
The dried single-network hydrogels, S2, S3, S6 and S8, were used as primary
network to prepare seqIPN hydrogels. All the primary networks were immersed in
ethanol solutions containing (50 wt% solid content) PEG-Al precursors, crosslinker
TMP-tris-thiol and initiator (3 wt%), the molar ratio of thiol to allyl was set to 1:1.
18
Experimental
The precursors in solutions were allowed to diffuse into the primary networks for 2
hours at 40 C. The excess of solution on the surface of primary network hydrogels
was removed with tissue paper and was placed in a Teflon mold covered by a glass
slide to prevent solvent evaporation. The secondary networks were allowed to
crosslink for 5 minutes under UV exposure (365nm, 28.5 mW/cm). The crosslinked
seqIPN hydrogels were dried in air overnight and then placed in a vacuum oven at
40 C for 1 hour. Figure 12 shows the scheme of seqIPN hydrogel preparation.
Figure 12. Preparation of seqIPN, using allyl functionalized PEG (Mn= 2k, 3k, 6k,
8k Da).
19
Experimental
Dense and loose single network, 2 kDa (S2) and 8 kDa (S8); hydrogels were used to
assess the diffusion time influence on mechanical properties of seqIPN hydrogels.
S2 and S8 hydrogels were immerged in the ethanol solution of PEG-Al precursors
(2 kDa and 8 kDa) with crosslinker TMP-tris-thiol and initiator (50 wt% solid
content) in an oven at 40C for 2h, 4h, 20h and 44 hours diffusion time. The
secondary networks were allowed to cure for 5 minutes under UV exposure (365
nm, 28.5 mW/cm2). All seqIPNs were prepared in 12 replicas with a thiol to allyl
molar ratio set to 1:1 with 3 wt% initiator to assess the properties at totally four
diffusion times. The cured seqIPN hydrogels with four different diffusion times
were dried in air overnight and then placed in a vacuum oven at 40C for 1 hour
respectively.
PEG 2kDa and 8 kDa were dissolved in EtOH to prepare 54.5 mg/mL and 138 mg/l
PEG solution with PEG-red-2k (0.05 wt%) and PEG-red-8k (0.01 wt%)
respectively. S2 and S8 hydrogels were immersed in a 1 mL PEG-red-2k and PEG-
red-8k solution respectively. A total of 24 pieces of samples were placed in an oven
at 40 C, the remaining solutions were used to analyse the PEG diffusion after 2, 4,
20, 25, 28 and 44 hours by UV/Vis absorption spectroscopy.
20
Experimental
Figure 13. Preparation of diffusion time dependent IPNs and semi IPN hydrogel
from 2 kDa and 8 kDa PEG.
Leaching tests were conducted to identify any unreacted starting materials and to
determine the gel fraction. The hydrogels were dried in the vacuum oven to remove
the solvent directly after curing, totally three replicas of each hydrogel sample
(thickness: 0.10 cm, length: 1.0 cm, width: 1.0 cm) were weighed (dry weight M)
and immersed in chloroform, one in deuterated chloroform for NMR analysis. All
21
Experimental
samples were swelled for 5 hours with three cycles of solvent exchange. The
leached hydrogels were dried overnight in air and placed in a 40C vacuum oven
for half hour to remove water and the dried weight was measured as M. The
leachate in deuterated chloroform was analyzed by NMR to determine remaining
functional groups. The gel fraction of the hydrogel was calculated by the following:
where M is the mass of the dry hydrogels after cure and M' is the mass of the dry
hydrogels after leaching.
Three or four replicas of each dried hydrogel were swollen in deionized water at
room temperature for 3 days to achieve equilibrium swelling. The degree of
swelling of hydrogels were measured after 5 min, 10 min, 20 min, 0,5 h, 1,5 h, 1
day, 2 days and 3 days. Totally three replicas were measured, the standard
deviations were marked with error bars in the swelling profile charts. The degree of
swelling was calculated as the following:
Degree of swelling = [(Wet weight Dry weight) / Dry weight] 100% (2)
The water content of hydrogels were calculated after the equilibrium swelling by
The molecular weight between cross-links (Mc), effective crosslinking density (),
and mesh size () were estimated according to the equilibrium swelling result.74
The water-induced volume-swelling ratio75 of hydrogel was calculated as:
22
Experimental
(4)
where v2,r is the volume fraction of polymer in the relaxed gel (hydrogels after cure,
before dry) and v2,s is the volume fraction polymer of swollen gel. These variables
are related to weight fractions by:
, (5)
[ ] (6)
and [ ] (7)
The structure evaluation is based on swelling and tensile tests result, the average
molecular weight between crosslinks (Mc) and mesh size () of PEG hydrogel were
calculated. Chain lengths between cross-links of PEG networks were assumed to
follow Gaussian distribution and the equilibrium swelling theory of Flory for
crosslinked polymers.
23
Experimental
The Mc,S was calculated with the following equation where S indicates swelling77
( ) ( ) ( )
(8)
( )( )
(9)
where v is Poisson's ratio. When the hydrogel material is fully swollen, its
mechanical behavior is similar to that of an incompressible rubber-like material.
Hence, the Poisson ratio of the hydrogels was assumed to be 0.5 in this work.80
Mc,T, where T indicates tensile stiffness,77 was calculated from the equation:
(10)
where C2,r is the mass concentration of polymer in solution before crosslinking (0.9
kg/l in ethanol, 0.86 kg/l in ethanol/butyl acetate mixture), is the gas constant
24
Experimental
(8.31 kPa l/mol K), and T is the temperature 298 K at which the tensile testing was
carried.
The crosslinking density c was determined 81 by:
(11)
The mesh size was then determined as the root-mean-square of the end-to-end
distance of the polymer chain in the unperturbed state is
(12)
where l is the average bond length (0.146 nm), is the characteristic ratio of the
82
polymer (typically 4.0 for PEG) and n is the number of repeating units in the
crosslink:
(13)
where is the molecular weight of the repeating unit (44 for PEG). The mesh size
can then be expressed as82
(14)
With the above expressions, structural evaluation of the molecular network can be
estimated by tensile measurements and swelling.
25
Experimental
The bacterial cellulose (BC) was obtained by cultivating the bacterium Acetobacter
in a pre-culture HS medium. This cultivating medium was prepared by pre-
cultivating Acetobacter aceti strain in the HestrinSchramm (HS) medium 27 for 7
days at 27 C. This pre-culture medium (5 mL) was used to inoculate 30 mL of
fresh HS medium for bacterium cultivation. The BC hydrogels were harvested after
7 days of culture at 27 C under static conditions. They were treated with 0.1 M
NaOH at 80C for 3 h and washed with de-ionized water. This process was repeated
3 times and the BC hydrogels were finally washed with de-ionized water for several
days until neutrality was reached. After the purified BC has been obtained, scissors
was used to cut the bacterial cellulose into 1x1x1 cm cubic shape and they were
then freeze-dried for 2 days to prepare the BC aerogels.
26
Experimental
The BC aerogels were used as templates for the preparation of fiber reinforced
DMA hydrogels. All BC aerogels were immersed in deionized aqueous solutions
containing 10, 40, 70 wt% DMA, respectively and initiator (5 wt%). The molar
ratio of DMA to PEGDA was set to 4 mol% for 10, 70 wt% DMA solution and 2
mol% to 40 wt% DMA solution. The solutions were allowed to diffuse into the BC
aerogels for one week at room temperature. Any excess of solutions on the surface
of the hydrogels were thereafter dried with a piece of tissue paper and the gels were
carefully placed into a Teflon mold with a glass slide on top to prevent solvent
evaporation. The DMA networks were allowed to crosslink with PEGDA for 10
minutes under Fusion UV irradiation belt with a total dose of 500 mJ/cm2, three
replicas of each samples were prepared for further analysis. One of three cured BC-
DMA replicas for each sample was subsequently freeze-dried for FT-Raman
analysis and gel fraction assess. The other 2 replicas were immersed in water for
one week to ensure the removal of any unreacted precursors and reaction residues,
water was changed several time each day. The purified hydrogels were dried in air
for 2 days and then placed in a vacuum oven at 40C overnight. Figure 15
illustrates the diagram of BC-DMA hydrogel formation.
27
Experimental
To obtain the gel fraction of DMA network a leaching study was conducted. One
replica of 3 samples freeze-dried BC-MDA hydrogel with mass (M) weighed (170
to 230 mg) including any unreacted starting materials was immersed in 200 mL of
deionized water. The deionized water was exchanged every day for one week. All
swollen hydrogels were air dried for 2 days and placed at 50C in a vacuum oven
overnight. The fully leached and dried sample mass M was recorded. The gel
fraction (crosslinking efficiency) of all samples was acquired from mass before and
after leaching using the formula below:
Content of the DMA network within the BC-DMA hydrogel was calculated from
the mass increase after leaching the samples from any unreacted precursors. In this
28
Experimental
case, the dried BC aerogel mass is marked as MBC, the dried BC-DMA mass is
marked as MBC-DMA, enabling the calculation of the secondary-network content:
Water content of the swollen DMA and BC-DMA hydrogels were collected on
three replicas. The hydrogel samples were dried in air for 2 days and further dried at
50C in vacuum oven overnight. The drying procedure was completed upon
reaching constant mass loss values. Then after the samples were immersed in
deionized water for one week and the wet weight of each sample was recorded, the
water content was calculated from the formula:
29
Results and Discussion
PEGs were functionalized with thiol (3 kDa to 8 kDa) (PEG-SH), allyl (3 kDa) (PEG-Al),
and methacrylate PEG (3 kDa). PEG based precursors were used to study the effect of
chain length, location of functional groups of PEGs, solvents, solid content of TEC
hydrogels. PEG-Al (2 kDa to 8 kDa) was prepared to study the effect of chain length on
single and seqIPN hydrogels. PEG-Al (2 kDa and 8 kDa) was prepared to study the effect
of diffusion time of seqIPN hydrogels. Additionally, PEGs (2 kDa and 8 kDa) were
decorated with disperse red 13 to probe the diffusion rate of PEGs in single-network
hydrogels. 1H NMR and 13
C NMR and MALDI-TOF were used to confirm the fully
functionalization of PEG precursors. FT-Raman revealed the S-H stretching peak at 2571
cm-1 and C=C stretching at 1645cm-1. The UV/Vis absorption spectrum of disperse red 13
evidenced a characteristic absorption peak at 503 nm.
All PEG hydrogels were prepared with a ratio of PEG functional group to crosslinker
functional group of 1:1 with 3wt% UV-initiator. The UV crosslinking of the three systems
was initially conducted in THF (56 wt%). The FT-Raman spectroscopy was used to assess
the conversion for P3-Al, P3-SH, and P3-MA after 1 minute UV-irradiation time. As
shown in Figure 16(I) there is no trace of the thiol stretching peak at 2570 cm-1 for the
PEG-SH hydrogel and no trace of allyl C=C stretching peak at 1645 cm-1 from PEG-Al
hydrogel, Figure 16 (II) and not for PEG-Ma hydrogel at 1645 cm-1, Figure 16 (III). The
30
Results and Discussion
31
Results and Discussion
Sample T-P3- T-P3- T-P3- E-P3- E/B-P3- E/B-P3- E-P3- E-P3- E-P6- E-P6- E-P8- E-P8- E-P8-
code Al-1 SH-1 Ma-1 Al-1 Al-1 Al-15 SH-1 SH-15 SH-1 SH-15 SH-1 SH-15 SH-30
Gel
fraction 68 72 - 95 92 97 99 99 99 99 99 99 99
(%)
The influence of solvent and solvent content using during polymerization on the hydrogel
network formation was studied. Table 3 presents the properties of hydrogels prepared with
56 wt% solid content. The hydrogel (E/B-P3-Al-1) prepared in EtOH/ butyl acetate
exhibits a tensile modulus of 444, which is much higher than the hydrogels prepared in
THF (T-P3-Al-1, 0.15 kPa). For hydrogels, PEG-Al system hydrogels E-P3-Al-1 revealed
higher mechanical properties compare to the same chain length PEG-SH hydrogels E-P3-
SH-1, which were assessed in this work. Because thiol-ene reaction has one side reaction
that is thiyl-thiyl radical coupling into disulfide, which was revealed to have more
influence of PEG-SH based hydrogels than PEG-Al based hydrogels. The disulfide
formation between PEG-SH based hydrogel E-P3-SH-1 (tensile moduli 139 kPa)
decreased the network density and demonstrated lower mechanical properties compare to
PEG-Al hydrogel E-P3-Al-1 (tensile moduli 311 kPa).
32
Results and Discussion
33
Results and Discussion
Table 4. Gel fraction (Gf), tensile modulus (E), stress-at-break (B), strain-at-break (B) of
PEG-SH hydrogels with 3k, 6k, 8k molecular weight and different UV irradiation times (1,
15, 30 minutes).
Hydrogel sample code UV-irradiation time Gf E B B
(minute) (%) (kPa) (kPa) (%)
E-P3-SH-1 1 99 139 127 127
E-P3-SH-15 15 99 104 89 126
E-P6-SH-1 1 99 2 9 171
E-P6-SH-15 15 99 20 15 95
E-P8-SH-1 1 99 3 - Over 200
E-P6-SH-30 30 99 17 20 153
E-P8-SH-15 15 99 2 4 169
E-P8-SH-30 30 99 3 6 177
The structural properties of a selection of hydrogel systems were evaluated using swelling
and tensile tests on the fully cured PEG-Al, PEG-SH (3 kDa and 6 kDa) hydrogels. As can
be seen in Table 5, the average molecular weight between crosslinks (Mc) for 3 kDa
system hydrogels prepared by PEG-Al is 1179 g/mol, which is a bit lower than PEG-SH,
ca. 1438 g/mol. For PEG-SH system, 6 kDa hydrogel E-P6-SH-15 Mc (2512 g/mol) is ca. 2
times higher than 3 kDa system. The volume-swelling ratio (from 2.7 to 8.6) and the mesh
size (4.8 to 11.7 nm) increased with increasing PEG chain length, from 3 kDa to 6 kDa, the
crosslinking density decreased from 10 to 4.1.
34
Results and Discussion
Table 5. The average molecular weight between crosslinks (Mc), volume-swelling ratio
(Q), crosslinking density (c), and mesh size () of PEG allyl and PEG thiol hydrogels.
Indices S and T denote whether the property was determined from swelling or from
tensile tests, respectively.
Hydrogel Mc,S Mc,T Q c,S c,T S T
The seqIPNs were introduced to the PEG hydrogel systems by diffusing secondary
networks into the crosslinked primary network. To prepare robust TEC PEG hydrogels,
PEG-Al system was used to crosslink with tri-thiol functionalized crosslinker (TMP-tir-
SH) for seqIPN hydrogel fabrication. Although the other TEC side reaction that is head to
head coupling of the carbon centred radicals from allyl could happen in PEG-Al system,
because of the auto-inhibition of the allylic compounds, this side reaction is much less
likely to happen during network formation.83
35
Results and Discussion
cm-1 in the cured hydrogel. Also in Table 6 evinces that the gel fraction reached 97% in all
single-network hydrogels, which correspond to the full TEC conversion.
Figure 17. FT-Raman spectra of 8 kDa PEG-Al and single-network hydrogel 2, 3, 6 and 8
kDa (S2, S3, S6 and S8).
Figure 18. (I), the tensile modulus and (II), degree of swelling of the single-network
hydrogel.
36
Results and Discussion
As shown in Figure 18 (I), the tensile modulus decreased from 555 to 175 KPa with
increasing PEG chain length from 2 kDa to 8 kDa, the water content of hydrogels
increased from 79 to 90% as the corresponding degree of swelling increased from 377 to
871%, Figure 18 (II). Table 6 details the relevant structure properties of the hydrogels
including the gel fraction based on the PEG-Al system and the average molecular weight
between crosslinks. As can be seen, the mesh size increased while the crosslinking density
decreased with increasing chain length of PEG precursors.
Table 6. Gel fraction (Gf), tensile modulus (E), stress-at-break (B), strain-at-break (B),
average molecular weight between crosslinks (Mc), mesh size (), volume-swelling ratio
(Q), crosslinking density (c) and mesh size () of single-network hydrogel. Indices S and
T indicate values determined from swelling or tensile tests, respectively.
Sample Gf E B B Q Mc,S Mc,T c,S10-4 c,T10-4 S T
code % (kPa) (kPa) (%) (g/mol) (g/mol) (mol/mL) (mol/mL) (nm) (nm)
S2 95 55518 226 65 2.3 766 902 15.5 13.2 3.7 4.0
S8 97 1751 121 102 4.6 3104 3407 3.8 3.5 9.5 9.9
37
Results and Discussion
Figure19. The FT-Raman spectra of PEG, crosslinker and dry hydrogels. a PEG-Al-8k, b
PEG-Al-8k with thiol corsslinker, c single-network hydrogel S8 and d seqIPN hydrogel 8-
8.
The FT-Raman spectra in Figure 19 show that the C=C vibrations of allyl group at 1640
cm-1 were not detected for the dried primary network S8 so as the seqIPN 8-8 hydrogels
based on 8 kDa PEG-Al. Table 7 demonstrates that the secondary-network gel fraction (Gf
II) was higher than 85%, which indicates that seqIPN hydrogels were successfully
prepared by TEC chemistry. The secondary-network solid content decreased with the
increasing chain length of the secondary-network precursor and decreasing primary
network mesh size. The volume fraction of relaxed hydrogel (vr) and volume fraction of
swollen hydrogel (vs) were used to calculate the volume-swelling ratio (Q) and apparent
crosslinking density (c,a). The Q value is increased and the crosslinking density decreased
with increasing secondary precursor chain length. These values indicate that the secondary
PEG network structure is also well controlled by the TEC chemistry.
The seqIPN hydrogel swelling kinetic were studied by measuring the degree of swelling
with time. Figure 20 depicts the degree of swelling as a function of time for the IPN
hydrogels based on different PEG chain length. The general trend for all IPNs is a reduced
swelling degree with the introduction of secondary networks based on shorter PEG chains.
38
Results and Discussion
Figure 20. Degree of swelling of seqIPN based on S8 hydrogel (a) based on S6 hydrogel
(b) based on S3 hydrogel (c) based on S2 hydrogel (d).
39
Table 7. SeqIPNs hydrogels primary network gel fraction (Gf I), secondary gel fraction (Gf II), the secondary (II) network mass
content and the degree of swelling, tensile modulus (E), stress at break (B), strain at break (B), volume fraction of relaxed
hydrogel (vr), volume fraction of swollen hydrogel (vs), volume swelling ratio (Q), apparent crosslinking density (c,a). *The
apparent crosslinking density is different from the crosslinking density calculated from Mc.
SeqIPN Primary Secondary Gf Gf II Swelling Water E B B vr vs Q c,a10-4
sample network network I II network (%) content (kPa) (kPa) (%) (mol/ml)
code (Da) (Da) (%) (%) solid (%)
content
(%)
8-2 8000 2000 97 95 34 58431 86 36560 12720 54 2 0.6 0.1 4.5 4.3
40
8-8 8000 8000 97 85 21 81013 89 20616 13217 8515 0.6 0.1 5.9 2.4
6-2
6-3 6000 3000 94 92 32 66112 87 31337 10619 4410 0.6 0.1 4.8 3.5
6-6 6000 6000 94 91 22 64623 89 35223 17431 6919 0.6 0.1 5.0 4.0
3-2 3000 2000 97 93 26 3979 80 59530 28320 6237 0.7 0.2 3.7 5.5
3-3 3000 3000 97 97 28 39012 80 58840 26477 5811 0.6 0.2 3.2 5.8
2-2 2000 2000 97 94 27 315 8 76 88950 29226 385 0.7 0.2 3.0 7.8
Results and Discussion
Figure 21 renders the overall plot of the tensile modulus and water content data for the
PEG chain influence on the seqIPN hydrogels.
Figure 21. The overall plot displaying the range of tensile modulus (top) and the water
content (bottom) of primary and seqIPNs hydrogels.
41
Results and Discussion
Figure 22. The FT-Raman spectra of PEG-Al-2k and diffusing time dependent IPN
hydrogels use S8 as primary network and PEG-Al-2k as secondary-network precursor (8-
2). The diffusion time of secondary-network precursor is shown in the brackets.
42
Results and Discussion
Figure 23. The secondary-network content and tensile modulus of IPN hydrogels (a) 8-2,
(b) 8-8 and degree of swelling of 8-2 (c) and 8-8 at different diffusion time.
In Table 8, the TEC reaction enabled efficient secondary network build up with excellent
gel fraction values of the secondary network (Gf II) of 84% and higher.
For the loosely crosslinked S8 system, in the case of the PEG 2 kDa secondary network,
Figure 23 (a), the percentage of solid content increased from 34% after 2 hours diffusion
(8-2:2) when compared to the maximum obtained level of 64% after 44 hours (8-2:44).
Remarkably, in Table 8, the tensile modulus was found to increase ca. 4 folds when
comparing the fully saturated IPN hydrogel (8-2:44) of 758 kPa with the primary network
S8 (175 kPa) and 2 folds in comparison to the unsaturated seqIPN (8-2:2; 365 kPa). These
results were further corroborated as can be seen in Table 8 by 3 folds enhanced stress-at-
43
Results and Discussion
break (B = 320 kPa) and 2 folds of strain-at-break values (B = 106%) for seqIPN 8-2:44
and in relationship to 8-2:2.
Figure 23 (c) displays the degree of swelling of 8-2 systems supressed by increasing
content of denser secondary network (2 kDa) in 8-2 system, which was the result of
increasing diffusion time. Figure 24 (c) shows that with the same crosslinking density of
primary and secondary network, the increasing secondary solid content still increased the
crosslinking density and decreased the degree of swelling.
44
Results and Discussion
Figure 24. The secondary-network content and tensile modulus of seqIPN hydrogels (a) 2-
2, (b) 2-8 and degree of swelling of 2-2 (c) and 2-8 at different diffusion time.
Similar diffusion behaviour was displayed for the 2 kDa secondary-network precursors
within densely crosslinked S2 primary network, Figure 24 (a) and (b). In Table 8, seqIPN
2-2:2 (with 2 hours diffusion time) exhibited 27% secondary-network solid content and
tensile moduli of 889 kPa. The maximum diffusion was reached after 44 hours and the
fabricated seqIPN 2-2:44 revealed a secondary-network solid content of 49% and a water
swelling capacity of 280%. The seqIPN 2-2:44 displayed the highest tensile modulus of
all fabricated networks with a value of 1135 kPa, which can be compared with the primary
network S2 of 555 kPa. Interestingly, the strain-at-break first decreased from 65% for S2
45
Results and Discussion
to 38% for the seqIPN 2-2:2 and then increased to 78% after 44 hours of diffusion (seqIPN
2-2:44).
For the 2-8 system, Figure 24 (b), is different from the other, since the secondary network
is looser than the primary network. From 2 to 44 hours diffusion time, secondary-network
content of seqIPN 2-8 increased from 8% and reached equilibrium to 22%. However, the
tensile modulus increased from S2, 555 kPa to 829 kPa with 8% secondary network and
dropped to 640 kPa with 22% secondary-network content.
The same suppression of degree of swelling is noticeable in Figure 24 (c) for seqIPN 2-2
system with increasing diffusion time and secondary-network content. For seqIPN 2-8,
Figure 24 (d) the degree of swelling depicts decreased and increased with increased
secondary-network content.
46
Table 8. Summary of properties of single and SeqIPN hydrogels including gel fraction (Gf I), secondary network precursor
diffusion time (Tdiffusion), secondary gel fraction (Gf II), secondary (II) network solid content (II%), the equilibrium degree of
swelling, tensile modulus (E), stress at break (B) and strain at break (B ).
47
8-8:20 8000 95 8000 20 34 84 6705 86 2901 1303 10211
8-8:44 8000 95 8000 44 38 84 66020 86 32430 2605 1104
S2 2000 97 - - - - 3804 79 55518 2261 655
2-2:2 2000 97 2000 2 27 94 3208 76 88950 29226 385
Results and Discussion
An overall plot of tensile modulus and water content is displayed in Figure 25.
Figure 25. The tensile modulus (top) and water content (bottom) of the seqIPNs with
different secondary-network diffusion time.
The diffusion rate of secondary-network precursors PEG-red 2 kDa and 8 kDa in PEG
hydrogels were traced by PEG-red (2 kDa and 8 kDa) and assessed by UV/Vis
spectrometry. Figure 26 displays the concentration of the remaining PEG-red in EtOH for
all semiIPNs, because of the single-network hydrogel absorption of the PEG-red, after 44
hours of diffusion the remaining PEG-red is less than the initial solution concentration,
after 2 hours of diffusion, an increase in the concentration are shown in most solutions. For
the PEG-red-8k, the equilibrium was reached after 20 hours of diffusion for the semi-2-8,
48
Results and Discussion
Figure 26. PEG-red-2k and PEG-red-8k remaining concentration in EtOH versus diffusion
time of semi-8-2, semi-8-8 and semi-2-2 and semi-2-8. UV/Vis absorption peak of PEG-
red at 503 nm.
Bacterial-cellulose (BC) aerogels were used as fiber reinforcement with DMA as monomer
and PEGDA as crosslinker in the preparation of BC-DMA hydrogels. As can be seen in
Figure 27 (a), SEM pictures reveal the fiber network of bacterial cellulose nanofibers.
Figure 27 (b) demonstrates a cross-section of BC aerogel and evidences the ca. 2 nm of
diameter and hundreds of micrometers in length of an individual nanofiber.
49
Results and Discussion
Figure 27. FE-SEM pictures of the freeze-dried BC microstructures (a) surface and (b)
cross section.
DMA hydrogel were also prepared as reference via FRP in aqueous solution under Fushion
UV cure system for 10 minutes. The hydrogels reached a water swelling equilibrium after
one week of swelling and seven solvent exchanges to remove any unreacted residues. The
FT-Raman spectra of cured DMA hydrogels are shown in Figure 28 (a). The C=C
vibrations at 1615-1661 cm-1 from unreacted DMA monomer or PEGDA crosslinker were
not detected in the dried hydrogels, supporting a high reaction conversion i.e. below the
detection limit using FT-Raman. For the BC-DMA hydrogels, there is a small trace of the
cellulose peaks from BC at 1157 - 1095 cm-1 in the FT-Raman spectra due to the small
fraction of BC present in the sample.
50
Results and Discussion
Figure 28, (a) The FT-Raman spectra of DMA and PEGDA, dry DMA hydrogel P-1, P-2,
P-3 and BC, dry BC-DMA hydrogel F-P-1, F-P-2 and F-P-3. (b) Photo of (I) swollen and
The gel fraction, compression modulus and other properties are presented in Table 9. With
the same crosslinker molar ratio (4 mol%) and the DMA monomer concentration
increasing from 10% (P-1) to 70% (P-3), the water content decreased from 92% to 77%,
51
Results and Discussion
which indicates that P-3 has a higher crosslinking density than P-1. However, with the
DMA monomer concentration increasing from 10% to 40% but crosslinker molar ratio
decreasing from 4 mol% (P-1) to 2 mol% (P-2), the water content still decreased from 92%
to 85%, which also gave evidence of the higher crosslinking density. These could due to
the network formation of FRP is random, the initial monomer concentration exhibits more
dominant effect of crosslinking density compared to crosslinker concentration.84 The
higher initial DMA monomer concentrations showed the higher crosslinking density of the
cured DMA hydrogels.85,86
Table 9. Sample code and properties of DMA hydrogels and BC-reinforced DMA
hydrogels: gel fraction (Gf), concentration (wt%) of DMA monomer, crosslinker
(PEGDA) molar ratio (mol%) to DMA, BC fiber content in DMA monomer and
crosslinker aqueous solution (BCas), DMA network content, BC fiber content in swollen
BC-DMA hydrogel (BCBC-DMA), equilibrium water content, and compression modulus (Ec).
Sample DMA PEGDA BCas Gf DMA- BCBC-DMA Water Ec
code (wt%) (mol%) (wt%) (%) network (wt%) content (MPa)
content (%)
(wt%)
P-1 10 4 0 94 8 - 92 1.0
P-2 40 2 0 93 15 - 85 1.0
P-3 70 4 0 - 23 - 77 2.9
F-P-1 10 4 1 94 13 8 78 4.4
F-P-2 40 2 1 94 23 5 75 5.3
F-P-3 70 4 1 95 30 3 70 8.3
As presented in Table 9, although the initial BC fiber content is the same for all the
samples (1%), the cured and swollen BC-DMA hydrogel fiber content is decreased from
8% to 3% with the DMA network content increased from 13% to 30%. Due to the limited
expansion of swollen BC network, the higher crosslinking density and wt% of DMA
network in BC-DMA hydrogel, the water content of BC-DMA hydrogels have been
52
Results and Discussion
suppressed ca. 10% compared with pure DMA hydrogels (92% to 77%) with the same
polymer-crosslinking density.
In Table 9, while the initial DMA wt% increased from 10 to 70 wt%, the compression
modulus (Ec) of DMA hydrogels increased from 1 to 2.9 MPa without BC. The Ec of BC-
DMA increased from 4.4 to 8.3 MPa with the DMA wt% increased from 10 to 70 wt% (4
mol% PEGDA). Ec of BC-DMA hydrogel increased ca. 3 times compared with the DMA
hydrogel with the same crosslinking density. However, increasing DMA from 10 to 40
wt% and decreasing PEGDA from 4 to 2 mol%, the BC-DMA exhibits an increase Ec from
4.4 to 5.3 MPa. Further presents the increasing initial DMA wt% will increase the
crosslinking density even with less crosslinker mol%.
DMA hydrogels also contributed with improved shear modulus and changed the water
absorption of BC hydrogels. Figure 29, (I) depicts the shear storage modulus G of BC-
DMA hydrogels and BC hydrogel. Shear modulus of BC without polymer network is close
to 0 kPa but after curing the DMA network in the BC network, the G of the resulting IPN
hydrogel P-F-3 increased up to ca. 350 kPa. The combination of DMA and BC fibers
locked water in the voids of the BC aerogel, as shown in Figure 29 (II) a, with a finger
force twisting the re-swollen BC hydrogel, water can be squeezed out. Water in swollen
BC-DMA hydrogels (Figure 30 (II) b) on the other hand, can only be removed by
evaporation and not by physical force.
53
Results and Discussion
Figure 29. I (a): the photo of BC hydrogel and (b): BC-DMA hydrogel under a finger
shear force. II: the shear storage modulus G (kPa) of re-swollen BC hydrogel, BC-DMA
SEM. As can be seen in Figure 30, after DMA network cured in the BC aerogels, the
composites of BC fibers and DMA networks show no trace of individual BC fiber compare
to raw BC aerogel, Figure 27. The FE-SEM pictures reveal that there is no trace of phase
separation between fiber and polymer networks of the BC-DMA hydrogels surface, Figure
30 (a), (b), (c), and cross section, Figure 30 (a), (b), (c); also, the pore size of the
hydrogels decreased from the loose crosslinked BC-DMA hydrogel F-P-1 (10 wt% DMA
and 4 mol% PEGDA) to densely crosslinked BC-DMA hydrogel F-P-3 (70 wt% DMA and
4 mol% PEGDA).
54
55
Results and Discussion
Figure 30. FE-SEM pictures of BC-DMA hydrogel surface of BC-DMA hydrogel F-P-1 (10 wt% DMA and 4 mol%
PEGDA), F-P-2 (40 wt% DMA and 2 mol% PEGDA), and F-P-3 (70 wt% DMA and 4 mol% PEGDA): a, b, c and cross
section a, b and c.
Conclusions
5 CONCLUSIONS
The purpose of this work was to relate and evaluate hydrogel fabrication parameters with
swelling and mechanical properties.
PEG single and sequential interpenetrating polymer network (seqIPN) hydrogels were
successfully prepared and characterized in this work via UV-initiated thiol-ene coupling
(TEC) chemistry.
A library of PEG hydrogels was prepared using PEG-SH or the reversed PEG-Al
precursors in combination with trifunctional crosslinkers. The UV-initiated TEC reaction
proved to be robust for the formation of PEG hydrogels under benign experimental
conditions. The type of solvent, solid content in solution, functional group and PEG chain
length were found to have direct influence on mechanical properties of PEG hydrogels.
Fabricated hydrogels based on PEG-Al displayed stronger mechanical properties than
PEG-SH hydrogels.
Well-defined PEG seqIPN with controllable mechanical properties have also been
prepared and assessed. Properties of a library of seqIPN hydrogel were compiled based on
the information of secondary-network content, gel fraction, swelling kinetic, mechanical
properties and structure evaluations. The seqIPN hydrogels based on the PEG-Al systems
showed 84% and higher gel fraction. The mechanical properties of PEG hydrogel were
increased to reach a tensile modulus over 1 MPa (2-2:44). The range of tensile modulus is
extended from single network, range from 175 kPa to 555 kPa, from seqIPN 365 kPa to
1135 KPa. Water content of PEG hydrogels was supressed by seqIPN from single network,
range 90% to 79% (degree of swelling 870% to 380%), to seqIPN 88% to 74% (degree of
swelling 580% to 280%).
56
Conclusions
The diffusion rate of the disperse red 13 decorated linear PEG with short chain (2 kDa) and
long chain (8 kDa) was evaluated in both a dense (2 kDa) and loose (8 kDa) PEG
crosslinked network.
57
Future work
6 FUTURE WORK
IPN is an effective way to manipulate mechanical properties of PEG hydrogels. Triple and
multiple networks of PEG IPN will be the next interesting hydrogel to prepare by TEC.
Combining polyDMA with PEG TEC hydrogels could achieve even higher mechanical
properties.
In order to further explore the potential of TEC chemistry for well-defined hydrogel
preparation, it will be interested to compare dendronized PEG with allyl groups with linear
PEG-Al. The mechanical properties will be expected to improve a lot because of the much
higher crosslinking density.
Dendronized PEG with thiol groups could crosslink without using crosslinker or
dissolution in a solvent.
58
Acknowledgements
7 ACKNOWLEDGEMENTS
I would like to thank my supervisors: Prof. Anders Hult is thanked for giving me the
chance to be a PhD student at KTH. Prof. Lars Berglund is thanked for being my co-
supervisor in the first 2 years. Associate prof. Michael Malkoch is thanked for teaching me
from laboratory safety to writing paper and helping me to become a PhD.
All seniors in the department of fiber and polymer technology are thanked for their help.
Thanks to members of biocomposite group. Prof. E. Kristofer Gamstedt and associate prof.
Qi Zhou are thanked for their helps.
The China Scholarship Council (CSC) and the Department of Fiber and Polymer
Technology at KTH are acknowledged for financial support.
Prof. Ling Wang from Chengdu University of Technology is thanked for supporting my
application of CSC scholarship during my master study.
Thanks to members of the coating group: special thanks to Marie, Yvonne for checking my
writings and giving a lot of help when I just arrived in the group. Hui is thanked for
working together with me for my papers and being a nice friend. Kim is thanked for a lot
59
Acknowledgements
of help in the lab. Jan is really thanked for supporting me with the materials to work for the
paper. Oliver, Jonas and Kristina are thanked for helping me with the Swedish abstract
writing. Mats K.G.J is thanked for checking my last paper and being tomten. Linda is
thanked for being so nice and reviewing my thesis. Camilla is thanked for her nice talks
and warm care. Alireza, Assya and Susanne are thanked for being good office-roommates.
Stacy is thanked for her happy personality. Andreas Fall is thanked for helping me with the
rheometer. Inger is greatly thanked for her help in the department. Big thanks to Eva,
Anna, Emma L, Emma , Bella, Hanna, Sara, Linn, Christian, Carl, Marcus, Martin,
Mauro, Pontus, Carmen, Eric and Petra.
Special thanks to my uncle Jiebing Li and Aunt Yun Yang in Sweden for helping me in
every aspect of my life. Yitong is thanked for her relax outlook on life. Jesper is thanked
for all the fun art things and taping for my niece. Jingyu is thanked for her nice entertain
in Japan and help me a lot in the wedding. Big thanks for Andong Liu, Aihua Pei, Yafang
Yan, Yingzhi Zhu, Wenbin Yu, Xueyu Du, Hongli Zhu, Bi Ran, Lingquan Deng, Yujia
Zhang, Jiayi Yang, Lin Li, Bo Yin, Liming, Zhiqiang Zheng, Chun Ying Shean, Andrew
M., Raquel, Lage, Dany, Pedro and other friends in Sweden, I thank all of you for the
happy moments.
Till familjen, Anders Nilsson (Fluffy) tackas fr att vara en omtnksam make; till Rositha,
Leif, Bosse, Elvy, Birgit, Kerstin, Lasse, Ammi, Lisbeth, Michael, Jenny, Stefan, tackas!
60
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