Jinxin Guo

Non-local photo-polymerization kinetics including multiple termination mechanisms and dark reactions: Part III. Primary radical generation and inhibition

Photopolymers are playing an ever more important role in diverse areas of research such as holographic data storage, hybrid photonic circuits, and solitary waves. In each of these applications, the production of primary radicals is the driving force of the polymerization processes. Therefore an understanding of the production, removal, and scavenging processes of free radicals in a photopolymer system is crucial in determining a material’s response to a given exposure. One such scavenging process is inhibition. In this paper the non-local photo-polymerization driven diffusion model is extended to more accurately model the effects of (i) time varying primary radical production, (ii) the rate of removal of photosensitizer, and (iii) inhibition. The model is presented to specifically analyze the effects of inhibition, which occur most predominantly at the start of grating growth, and comparisons between theory and experiment are performed which quantify these effects.

Non-local spatial frequency response of photopolymer materials containing chain transfer agents: II. Experimental results

In part I of this paper the non-local photo-polymerization driven diffusion model was extended to include the kinetics of chain transfer and re-initiation, in order to analyse the effects of chain transfer agents on the system kinetics and to study their use in reducing the average polymer chain length in free-radical based photopolymer materials. Based on these results, it is proposed that one possible way to improve the material response at high spatial frequency is the addition of chain transfer agents. In this paper, the validity of the proposed model is examined by applying it to fit experimental data for an acrylamide/polyvinyl alcohol (AA/PVA) layer containing two different types of chain transfer agent (CTA): sodium formate (HCOONa) and 1-mercapto-2-propanol (CH3CH(OH)CH2SH). The effects on decreasing the average polymer chain length formed, by the addition of chain transfer agent, which in turn reduces the non-local response of the material, are demonstrated. These reductions are shown to be accompanied by improved high spatial frequency response. Key material parameters are extracted by numerically fitting experimentally measured refractive index modulation growth curves using the model. Further independent experimental confirmation of the reduction in the average polymer molecular weight is provided using a diffusion based holographic technique.

A Review of the Optimisation of Photopolymer Materials for Holographic Data Storage

Photopolymers are very interesting as optically sensitive recording media due to the fact that they are inexpensive, self-processing materials with the ability to capture low-loss, high-fidelity volume recordings of 3D illuminating patterns. We have prepared this paper in part in order to enable the recognition of outstanding issues, which limit in particular the data storage capacity in holographic data storage media. In an attempt to further develop the data storage capacity and quality of the information stored, that is, the material sensitivity and resolution, a deeper understanding of such materials in order to improve them has become ever more crucial. In this paper a brief review of the optimisation of photopolymer materials for holographic data storage (HDS) applications is described. The key contributions of each work examined and many of the suggestions made for the improvement of the different photopolymer material discussed are presented.

Optimisation of photopolymers for holographic applications using the Non-local Photo-polymerization Driven Diffusion model

An understanding of the photochemical and photo-physical processes, which occur during photopolymerization is of extreme importance when attempting to improve a photopolymer materials performance for a given application. Recent work carried out on the modelling of the mechanisms which occur in photopolymers during- and post-exposure, has led to the development of a tool, which can be used to predict the behaviour of these materials under a wide range of conditions. In this paper, we explore this Non-local Photo-polymerisation Driven Diffusion model, illustrating some of the useful trends, which the model predicts and we analyse their implications on the improvement of photopolymer material performance.

Quantitative Comparison of Five Different Photosensitizers for Use in a Photopolymer

Several studies of the time varying photon absorption effects, which occur during the photoinitiation process involving in photopolymer materials, have been presented. Three primary mechanisms have been identified: (i) the dye absorption, (ii) recovery, and (iii) bleaching. Based on an analysis of these mechanisms, the production of primary radicals can be physically described and modelled. In free radical photopolymerization systems, the excited dye molecules induce the production of the primary radicals, 𝑅•, which are key in determining how many monomers are polymerized. This, in turn, is closely related to the refractive index modulation formed during holographic recording. In this paper, to avoid the complexities involved in estimating the rate constant of intersystem crossing, 𝑘𝑠𝑡, in going from the excited singlet state dye to the excited triplet state dye, we introduce two rates, 𝑘𝑎𝑆 and 𝑘𝑎𝑇 these are the proposed rate constants of photon absorption in going from the ground state to the singlet and triplet states, respectively. Using the resulting model, four kinds of Xanthene dyes: Erythrosin B; Eosin Y; Phloxine B, Rose Bengal, and one Thiazine dye: Methylene Blue, are experimentally characterised for use in an AA/PVA photopolymer.

Non-local spatial frequency response of photopolymer materials containing chain transfer agents: I. Theoretical modelling

The non-local photopolymerization driven diffusion (NPDD) model predicts that a reduction in the non-local response length within a photopolymer material will improve its high spatial frequency response. The introduction of a chain transfer agent reduces the average molecular weight of polymer chains formed during free radical polymerization. Therefore a chain transfer agent (CTA) provides a practical method to reduce the non-local response length. An extended NPDD model is presented, which includes the chain transfer reaction and most major photochemical processes. The addition of a chain transfer agent into an acrylamide/polyvinyl alcohol photopolymer material is simulated and the predictions of the model are examined. The predictions of the model are experimentally examined in part II of this paper.

Nanoparticle polymer composite volume gratings incorporating chain transfer agents for holography and slow-neutron optics

We demonstrate twofold enhancement of the saturated refractive index modulation (Δn(sat)) recorded in a photopolymerizable nanoparticle-acrylate polymer composite film by incorporating thiols acting as chain transfer agents. The chain transfer reaction of thiols with (meth)acrylate monomer reduces the polymer crosslinking density and facilitates the mutual diffusion of nanoparticles and monomer during holographic exposure. These modifications provide increased density modulations of nanoparticles and the formed polymer, resulting in the enhancement of Δn(sat) as high as 1.6×10(-2) at a wavelength of 532 nm. The incorporation of thiols also leads to shrinkage suppression and to improvement of the gratings spatial frequency response. Such simultaneous improvement is very useful for holographic applications in light and neutron optics.

Study of photosensitizer diffusion in a photopolymer material for holographic applications

Photopolymer materials exhibit good characteristics when used as holographic recording media. Extensive studies have been carried out on the behavior of the various chemical components in such materials, with photosensitizers in particular receiving much attention. In all previous analysis of photopolymer kinetics, the effects of photosensitiser diffusion have been neglected. For rapid sequential holographic recordings in photopolymers, for example, in an application such as holographic data storage, dye diffusion effects may become more pronounced. Therefore, we examine the dye diffusion effects of erythrosine B in an acrylamide/polyvinyl alcohol material. This is achieved using simple experimental techniques and a proposed theoretical model.

Measurement of polymerization-shrinkage evolution during curing in photopolymer with a white-light Fabry-Pérot interferometer

We propose a simple method of measuring polymerization-shrinkage evolution during curing in photopolymer. The real-time spectral fringe analysis of a broadband beam transmitted through a Fabry-Pérot etalon supported by a photopolymer film provides the shrinkage evolution during curing. For the proof-of-principle demonstration a blue-sensitized nanoparticle-polymer composite material is used. It is shown that the measured shrinkage dynamics are well correlated with the photo-calorimetric conversion dynamics of monomer to polymer. We also discuss a discrepancy in steady-state shrinkage between our proposed and holographic Bragg-angle detuning measurements.

Effects of chain-transferring thiol functionalities on the performance of nanoparticle-polymer composite volume gratings

We report influences of varying functionalities of thiols as chain transfer agents on the spatial frequency response, polymerization shrinkage, and thermal stability of a volume grating recorded in a photopolymerizable ZrO₂ nanoparticle-polymer composite film. It is shown that a substantial increase in the saturated refractive index modulation is realized at high spatial frequencies by doping with multifunctional thiols. Moreover, the incorporation of multifunctional thiols considerably suppresses polymerization shrinkage of recorded volume gratings and thermal changes in refractive index and film thickness as compared with the case of mono-thiol. These results indicate that multifunctional thiols provide effective control of the properties of nanoparticle-polymer composite volume gratings for various applications in light and neutron optics.