Abstract
In order to tailor hydrogels for the application as actuator-sensor microsystems based on the responsive behaviour of smart gels, a general strategy has to be developed. Since the phase transition phenomenon of hydrogels is theoretically well understood advanced materials based on the predictions can be prepared. The requirements for applying hydrogels can be summarized as follows:
-
Development of novel sensitive polymers: Polymer networks with a large volume transition in combination with a sufficient high elastic modulus and short response times have to be prepared.
-
Definition of the stimulus: Responsive behaviour of the gels towards relevant stimuli (e.g. temperature, pH value, solvent composition, low molecular weight solutes etc.) has to be realized. The hydrogels have to show a strong, non-linear response towards these stimuli. The defined adjustment of the stimuli must be possible.
-
Speed of response: The response time of the smart hydrogels have to be decreased by some orders of magnitude compared with conventional gels. Fast responsive hydrogels are necessary to obtain sufficient fast cycle times.
-
Specific stimulation: The subsequent adjustment of the transition by modification (e.g. changing the pH value) of the applied polymers must be possible. The external stimulation (e.g. by photo-switching) is desirable. Advanced materials will show multi-sensitive behaviour.
Since the volume phase transition of hydrogels is a diffusion-limited process the size of the synthesized hydrogels is an important factor. Consistent downscaling of the gel size will result in fast smart gels with sufficient response times. In order to apply smart gels in micro-systems, new preparation techniques for hydrogels have to be developed. For the up-coming nano-technology, nano-sized gels as actuating material would be of great interest.
An often applied method for the synthesis of hydrogels, especially for applications in medicine and pharmaceutics, is based on radiochemistry. The hydrogel can be formed by irradiation of monomers, polymers dissolved in water, or polymers in dry state. Electrons of different energies or γ-rays are used as high-energy radiation. The possibilities of the radiation-chemical synthesis of smart hydrogels are discussed on different examples. The technique is applied to bulk polymers, to micro- and nanogel particles, and to patterned layers on different materials. The basics and fundamentals of irradiation techniques as well as the equipment are described.
In addition to synthesis of hydrogels, the theory of thermoreversible gelation and the gel point itself, the determination of the gel point on gelatin by using dynamic light scattering (DLS), oscillatory shear rheology as well as nuclear magnetic resonance (NMR) diffusion experiments will be described. Special attention has been devoted to the comparison of the results each methods have been provided when monitoring the gelatin gelation process. Furthermore, an important point is the estimation of the critical dynamical exponents in DLS and rheology at the gel point and their comparison with the theoretical prediction, which was given by Doi and Onuki.
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Notes
- 1.
The term dose means here the quantity of radiation applied to or absorbed accidentally by a given volume or mass of sample. The absorbed dose is measured in Gray (Gy), 1 Gy = 1J/kg.
- 2.
The virtual dose is required for changing the MWD of the polymer in such a way that M w = 2 M n . If the polymer under investigation has a broader distribution, then D V > 0, or if it has a narrower distribution, then D V < 0.
- 3.
Co60 is formed in atomic reactors under the bombardment with neutrons: \({\rm Co}_{27}^{\quad 59} + {\rm n}_0^1 \to {\rm Co}_{27}^{\quad 60} + \gamma \)
- 4.
The term nanogel is used for intramolecularly cross-linked polymers. For intermolecularly cross-linked gels in the range of several 100 nm, the term microgel is used.
- 5.
The overlap concentration c* is that concentration where contacts between the polymer chains occur. c* depends on molecular weight; the higher M is, the smaller is c*. At c > c*, the polymer chains form an entanglement (physical) network with elastic properties. It can be destroyed by adding solvent.
- 6.
PAA: pKa = 4.7, Yu et al. (1992).
Abbreviations
- 2VP:
-
2-vinyl pyridine
- AAmPA:
-
3-acrylamido propionic acid
- ATR-FTIR:
-
Attenuated total reflection Fourier transform infra red
- DI:
-
De-ionized
- DLS:
-
Dynamic light scattering
- DMAAAm:
-
2-(dimethylamino)-N-ethyl acrylamide
- DMAAm:
-
N, N-dimethylacrylamide
- DMIAAm:
-
2-(dimethyl maleimido)-N-ethyl-acrylamide
- DSC:
-
Differential scanning calorimetry
- EBL:
-
Electron beam lithography
- FESEM:
-
Field emission scanning electron microscopy
- HCl:
-
Hydrochloric acid
- HPC:
-
Hydroxypropylcellulose
- LBG:
-
Locust bean gum
- LCST:
-
Lower critical solution temperature
- MBAAm:
-
N, N-methylene bisacrylamide
- MWD:
-
Molecular weight distribution
- NIPAAm:
-
N-isopropyl acrylamide
- NMR:
-
Nuclear magnetic resonance
- OWS:
-
Optical waveguide spectroscopy
- P2VP:
-
Poly(2-vinyl pyridine)
- P4VP:
-
Poly(4-vinyl pyridine)
- PAAc:
-
Poly(acrylic acid)
- PEO:
-
Poly(ethylene oxide)
- PFG-NMR:
-
Pulsed field gradient nuclear magnetic resonance
- PNIPAAm:
-
Poly(N-isopropyl acrylamide)
- PPO:
-
Poly(propylene oxide)
- PVA:
-
Poly(vinyl alcohol)
- PVCL:
-
Poly(vinyl caprolactam)
- PVDF:
-
Poly(vinyliden fluorid)
- PVME:
-
Poly(vinyl methyl ether)
- PVP:
-
Poly(vinyl pyrrolidone)
- SEM:
-
Scanning electron microscopy
- SPR:
-
Surface plasmon resonance
- TCF:
-
Time correlation function
- UV:
-
Ultraviolett
- XG:
-
Xanthan gum
- A :
-
Area
- c P :
-
Concentration of polymer solution
- d :
-
Diameter in equilibrium state
- d 0 :
-
Diameter at preparation
- d f :
-
Fractal dimension of the critical gel
- D :
-
Diffusion coefficient
- D :
-
Irradiation dose
- D av :
-
Average dose
- D g :
-
Gelation dose
- D p :
-
Fractal exponent
- D V :
-
Virtual dose
- g :
-
Gel fraction
- g 1(q,t):
-
Electric field correlation function
- g 2(q,t):
-
Time-intensity correlation function
- G(t):
-
Shear stress relaxation modulus
- G′(ω):
-
Shear storage modulus
- G″(ω):
-
Shear loss modulus
- I(t):
-
Scattering intensity at time t
- l :
-
Layer thickness
- l 0 :
-
Layer thickness in dry state
- M n :
-
Number-averaged molecular weight
- M w :
-
Weight-averaged molecular weight
- n :
-
Critical exponent in shear rheology
- n :
-
Refractive index
- p 0 :
-
Average number of main chain scissions per monomer unit and per unit dose
- q :
-
Scattering vector
- q 0 :
-
Proportion of monomer units cross-linked per unit dose
- Q :
-
Degree of swelling
- Q m :
-
Weight degree of swelling
- s:
-
Sol fraction
- S :
-
Gel stiffness
- S(q, t):
-
Dynamic structure factor
- t :
-
Time
- T :
-
Temperature
- T c :
-
Critical temperature
- T syn :
-
Synthesis temperature
- u 2,0 :
-
Weight-averaged degree of polymerisation of the polymer before irradiation
- U B :
-
Acceleration voltage
- V:
-
Volume in equilibrium state
- V 0 :
-
Volume at preparation
- W d :
-
Weight of dry network
- W t :
-
Weight of swollen network at time t
- β, μ :
-
Critical exponents in DLS
- ΔT c :
-
Width of temperature induced transition
- θ :
-
Scattering angle
- ω :
-
Shear frequency
- ω:
-
Rotational speed
- <τ>:
-
Mean relaxation time
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Acknowledgments
The authors are grateful to Dr. I. Mönch (IFW Dresden) for the ELB-experiments and to Dr. U. Gohs (IPF Dresden) for the irradiation experiments with the electron accelerator.
The financial support by the DFG (grants no. RI 1079/1-1, RI 1079/1-2) is gratefully acknowledged.
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Kuckling, D., Arndt, KF., Richter, S. (2009). Synthesis of Hydrogels. In: Gerlach, G., Arndt, KF. (eds) Hydrogel Sensors and Actuators. Springer Series on Chemical Sensors and Biosensors, vol 6. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-540-75645-3_2
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