Jeffrey W. Stansbury - Profile on Academia.edu (original) (raw)

Papers by Jeffrey W. Stansbury

Polymer Chemistry, 2020

Photopolymerizable semicrystalline thermoplastics resulting from thiol-ene polymerizations were f... more Photopolymerizable semicrystalline thermoplastics resulting from thiol-ene polymerizations were formed via fast polymerizations and achieved excellent mechanical properties. These materials have been shown to produce materials desirable for additive manufacturing (3D printing), especially for recyclable printing and investment casting. However, while well-resolved prints were previously achieved with the thiol-ene thermoplastics, the remarkable elongation at break (ϵ max ) and toughness (T) attained in bulk were not realized for 3D printed components (ϵ max,bulk ~ 790%, T bulk ~ 102 MJ m -3 vs. ϵ max,print < 5%, T print < 0.5 MJ m -3 ). In this work, small concentrations (5-10 mol%) of a crosslinker were added to the original thiol-ene resin composition without sacrificing crystallization potential to achieve semicrystalline, covalently crosslinked networks with enhanced mechanical properties. Improvements in ductility and overall toughness were observed for printed crosslinked structures, and substantial mechanical augmentation was further demonstrated with post-manufacture thermal conditioning of printed materials above the melting temperature (T m ). In some instances, this thermal conditioning to reset the crystalline component of the crosslinked prints yielded mechanical properties that were comparable or superior to its bulk counterpart (ϵ max ~ 790%, T ~ 95 MJ m -3 ). These unique photopolymerizations and their corresponding monomer compositions exhibited concurrent polymerization and crystallization along with mechanical properties that were tunable by changes to the monomer composition, photopolymerization conditions, and post-polymerization conditioning. This is the first example of a 3D printed semicrystalline, crosslinked material with thermally tunable mechanical properties that are superior to many commercially-available resins.

Physics Today, Apr 1, 2008

European Polymer Journal, Feb 1, 2011

The resin phase of dental composites is mainly composed of combinations of dimethacrylate comonom... more The resin phase of dental composites is mainly composed of combinations of dimethacrylate comonomers, with final polymeric network structure defined by monomer type/reactivity and degree of conversion. This fundamental study evaluates how increasing concentrations of the flexible triethylene glycol dimethacrylate (TEGDMA) influences void formation in bisphenol A diglycidyl dimethacrylate (BisGMA) co-polymerizations and correlates this aspect of network structure with reaction kinetic parameters and macroscopic volumetric shrinkage. Photopolymerization kinetics was followed in real-time by a near-infrared (NIR) spectroscopic technique, viscosity was assessed with a viscometer, volumetric shrinkage was followed with a linometer, free volume formation was determined by positron annihilation lifetime spectroscopy (PALS) and the sol-gel composition was determined by extraction with dichloromethane followed

Macromolecules, Jul 21, 2007

This study focuses on the design and development of novel monovinylic (meth)acrylate monomers wit... more This study focuses on the design and development of novel monovinylic (meth)acrylate monomers with enhanced polymerization kinetics and the evaluation of their performance as reactive diluents in diacrylate systems. Novel (meth)acrylic monomers characterized by several new secondary functionalities are developed in this study and are shown to exhibit reactivities 10-70 fold greater than traditional monoacrylates such as hexyl acrylate. These monomers were designed based on our understanding of interactions between monomer structure, polymerizations kinetics, and polymer properties. Performance of these monovinyl monomers as reactive diluents is also investigated in this study. Copolymerization of these monomers with diacrylates enhanced both the reactivity and the mechanical properties of the diacrylate system. Specifically, while copolymerization of a diacrylate system with traditional monoacrylates such as hexyl acrylate decreases the overall reactivity of the system, its copolymerization with the novel monomers led to comonomer mixtures, that were 30-50% more reactive than either of the individual components, with initial polymerization rates increased by as much as 2 times the more reactive component. Further, the copolymerization of these novel monovinyl systems with diacrylates also enabled formation of polymers with enhanced mechanical properties over the corresponding diacrylates including a more homogeneous network structure as indicated by a glass transition temperature that was narrowed by up to 55 % while increasing the glass transition temperature by as much as 10°C.

European Polymer Journal, Jun 1, 2015

This work presents an approach to extend the period for phase separation, independent of temperat... more This work presents an approach to extend the period for phase separation, independent of temperature, in ambient phase-separating photopolymerizations based on the copolymerization of structurally similar mono-and di-vinyl monomers. Copolymer resins composed of triethylene glycol dimethacrylate (TEGDMA) and ethylene glycol methyl ether methacrylate (EGMEMA) were modified with a thermoplastic prepolymer, poly(butyl methacrylate). With increasing EGMEMA modification into the bulk TEGDMA resin, there is a decrease in the initial reaction rate, which increases the time for development of compositionally different phases prior to network gelation. The period between phase separation and gelation was probed through optical and rheological measurements, and it was extended from 22 s in a TEGDMA resin to 69 s in a TEGDMA:EGMEMA copolymer, allowing these materials to be processed under a wide range of UV-irradiation intensities (300 µW cm -2 -100 mW cm -2 ), which provided an additional degree of control over the resulting phase separated domain size and morphology.

Polymer Chemistry, 2014

Photo-reactive nanogels with an integrated photoinitiator-based functionality were synthesized vi... more Photo-reactive nanogels with an integrated photoinitiator-based functionality were synthesized via a Reversible Addition-Fragmentation Chain Transfer (RAFT) process. Without additional free initiators, this nanogel is capable of radical generation and initiating polymerization of a secondary monomer (i.e. dimethacrylate) that infiltrates and disperses the nanogel particles. Due to the presence of RAFT functionality and the fact that all initiating sites are initially located within the nanogel structure, gelation can be delayed by sequencing the polymerization from the nanogel to the bulk matrix. During polymerization of a nanogel-filled resin system, a progressive delay of gelation conversion from about 2 % for conventional chain growth polymerization to 18 % for the same monomer containing 20 wt% nanogel additive was achieved. A significant delay of stress development was also observed with much lower final stress achieved with the nanogelmodified systems due to the change of network formation mechanics. Compared with the nanogelfree dimethacrylate control, which contained uniformly distributed free initiator, the flexural modulus and mechanical strength results were maintained for the photopolymers with nanogel contents greater than 10 wt%. There appears to be a critical interparticle spacing of the photoreactive nanogel that provides effective photopolymerization while providing delayed gelation and substantial stress reduction.

Polymer, Mar 1, 2007

The development of thiol-ene/thiol-epoxy hybrid networks offers the advantage of tailorable polym... more The development of thiol-ene/thiol-epoxy hybrid networks offers the advantage of tailorable polymerization kinetics while producing a highly crosslinked, high T g polymer that has significantly reduced shrinkage stress. Stoichiometric mixtures of pentaerythritol tetra(3-mercaptopropionate) (PETMP)/triallyl-1,3,5-triazine-2,4,6-trione (TATATO) (thiol-ene, mixture 1) and PETMP/ bisphenol a diglycidyl ether (BADGE) (thiol-epoxy, mixture 2) were prepared and hybrid mixtures of 75/25, 50/50, 25/75, and 10/90 w/w of mixtures 1 and 2 were polymerized using a combination of both radical and anionic initiation. The light exposure timing and the relative initiation conditions of the two types were used to control the order and relative rates of the radical and anionic polymerizations. The 50/50 w/w thiol-ene/thiol-epoxy hybrid material exhibited a final stress of only 0.2 MPa, which is 90 % lower than the stress developed in a control dimethacrylate resin. Kinetic analysis indicates composition affects network development in thiol-ene/thiol-epoxy hybrid networks and produces materials with robust mechanical properties.

Dental Materials Journal, 2007

The aim of this study was to develop an effective primer to improve the adhesive property between... more The aim of this study was to develop an effective primer to improve the adhesive property between all kinds of dental metal alloy and resin cement. To this end, we synthesized N,N'-dimethacryloylcystine (NDMCC) which had both disulfide functional group (to improve adhesion between precious metal alloy and resin) and carboxyl group (to improve adhesion between non-precious metal alloy and resin). With the presence of SuperBond C&B, the adhesion between precious, semi-precious, and non-precious dental metal alloys and resin cement was improved when compared to the untreated controls. However, the adhesive property between all types of dental metal alloy and resin cement was not improved with Panavia 21EX. In particular, reduced bond strength in the case of non-precious metal alloy was speculated to arise from the acid-base neutralization reaction between the carboxyl group of NDMCC and the amine present in the polymerization initiator system of Panavia 21EX.

Journal of Applied Polymer Science, May 6, 2014

A mechanism for polymerization shrinkage and stress reduction was developed for heterogeneous net... more A mechanism for polymerization shrinkage and stress reduction was developed for heterogeneous networks formed via ambient, photo-initiated polymerization-induced phase separation (PIPS). The material system used consists of a bulk homopolymer matrix of triethylene glycol dimethacrylate (TEGDMA) modified with one of three non-reactive, linear prepolymers (polymethyl, ethyl and butyl methacrylate). At higher prepolymer loading levels (10-20 wt%) an enhanced reduction in both shrinkage and polymerization stress is observed. The onset of gelation in these materials is delayed to a higher degree of methacrylate conversion (~15-25%), providing more time for phase structure evolution by thermodynamically driven monomer diffusion between immiscible phases prior to network macro-gelation. The resulting phase structure was probed by introducing a fluorescently tagged prepolymer into the matrix. The phase structure evolves from a dispersion of prepolymer at low loading levels to a fully co-continuous heterogeneous network at higher loadings. The bulk modulus in phase separated networks is equivalent or greater than that of poly(TEGDMA), despite a reduced polymerization rate and cross-link density in the prepolymer-rich domains.

Polymer Chemistry, 2017

A new addition-fragmentation chain transfer (AFT) capable moiety was incorporated into a dimethac... more A new addition-fragmentation chain transfer (AFT) capable moiety was incorporated into a dimethacrylate monomer that participated readily in network formation by copolymerizing with multifunctional methacrylates or acrylates. The process of AFT occurred simultaneously with photopolymerization of the AFT monomer (AFM) and other (meth)acrylate monomers leading to polymer stress relaxation via network reconfiguration. At low loading levels of the AFM, a significant reduction in shrinkage stress, especially for acrylate monomers, was observed with nominal effects on conversion. At higher loading levels of the AFM, the photopolymerization reaction kinetics and final double bond conversion were significantly lowered along with a delay in the gel-point conversion. Electron paramagnetic resonance studies during polymerization revealed the presence of a distinct radical species that was present in proportional quantities to the AFM content in the system. The lifetime and the character of the persistent radicals were altered due to the presence of the distinctive radical, in turn affecting the polymerization kinetics. With polymerization conducted at higher irradiance, the differential conversion between the control resin and samples with moderate AFM content was minimal, especially for the methacrylate-based formulations.

Polymer, Sep 1, 2012

Non-reactive, thermoplastic prepolymers (poly-methyl, ethyl and butyl methacrylate) were added to... more Non-reactive, thermoplastic prepolymers (poly-methyl, ethyl and butyl methacrylate) were added to a model homopolymer matrix composed of triethylene glycol dimethacrylate (TEGDMA) to form heterogeneous networks via polymerization induced phase separation (PIPS). PIPS creates networks with distinct phase structure that can partially compensate for volumetric shrinkage during polymerization through localized internal volume expansion. This investigation utilizes purely photo-initiated, free-radical systems, broadening the scope of applications for PIPS since these processing conditions have not been studied previously. The introduction of prepolymer into TEGDMA monomer resulted in stable, homogeneous monomer formulations, most of which underwent PIPS upon photo-irradiation, creating heterogeneous networks. During polymerization the presence of prepolymer enhanced autoacceleration, allowing for a more extensive ambient cure of the material. Phase separation, as characterized by dynamic changes in sample turbidity, was monitored simultaneously with monomer conversion and either preceded or was coincident with network gelation. Dynamic mechanical analysis shows a broadening of the tan delta peak and secondary peak formation, characteristic of phase-separated materials, indicating one phase rich in prepolymer and another depleted form upon phase separation. In certain cases, PIPS leads to an enhanced physical reduction of volumetric shrinkage, which is attractive for many applications including dental composite materials.

Polymer, Jul 1, 2011

Chain-transfer reactions from thiols to methacrylates are expected to delay gelation and possibly... more Chain-transfer reactions from thiols to methacrylates are expected to delay gelation and possibly reduce stress at the bonded interface of dental restorations. Thiol additives with varying structures were combined with a dimethacrylate commonly used in dental materials. Polymerization stress/ modulus development were monitored by a tensometer/rheometer, respectively, both coupled with RT-NIR. For all thiol-modified materials, conversion and modulus were 5-25 % higher than the control, and maximum reaction rate was 25-50 % lower. Gel point conversions were 12-22 % (control=5 %), and deceleration was observed at later stages in conversion (30-60 %; control=15 %). Consequently, even with increased conversion/modulus, stress values were either equal or reduced compared to the control. This approach does not require any modification in the bonding/ photoactivation procedures, and seems promising for stress management not only in polymeric dental materials, but also for other applications of glassy, crosslinked photopolymers, as long as thiol volatility is addressed.

Dental Materials, Nov 1, 2014

Objectives-This study examines how nanogel structure correlates with photopolymerization and key ... more Objectives-This study examines how nanogel structure correlates with photopolymerization and key polymer properties upon addition of nanogels with latent reactivity into a monomer dispersant to produce polymer/polymer composites. Methods-Two nanogels that retained RAFT functionality based on the synthetic approach were prepared to have different branching densities. These reactive nanogels were dispersed in triethylene glycol dimethacrylate at 0-40 wt%. Reaction kinetics, volumetric shrinkage and shrinkage stress associated with the photopolymerization of nanogel-modified formulations were measured in real time with mechanical properties of the polymers also evaluated. The basic structure of RAFT-derived nanogel particles was examined by the preparation of a separate nanogel constructed with degradable disulfide crosslinking groups. The model nanogel molecular weight and polydispersity were compared before and after degradation. Results-Despite the controlled radical synthetic approach, the nanogels, which are composed of multiple interconnected, short primary chains presented relatively high polydispersity. Through addition of the reactive nanogels to a monomer that both infiltrates and disperses the nanogels, the photopolymerization rate was moderately reduced with the increase of nanogel loading levels. Volumetric shrinkage decreased proportionally with nanogel concentration; however, a greater than proportional reduction of polymerization-induced stress was observed. Mechanical properties, such as flexural strength, storage modulus were maintained at the same levels as the control resin for nanogel systems up to 40 wt%.

Macromolecules, Nov 11, 2008

The tremendous diversity of materials properties available with polymers is due in large part to ... more The tremendous diversity of materials properties available with polymers is due in large part to the ability to design structures from the monomeric state. The ease of use of comonomer mixtures only expands this versatility. While final polymer properties are obviously important in the selection or development of a material for a given purpose, for a number of applications, such as optical fiber coatings, photolithography and microelectronics, the additional requirement of a very rapid polymerization process may be equally critical. A class of unusually reactive mono-(meth)acrylate monomers bearing secondary functionality that includes carbonates, carbamates and oxazolidones, has been demonstrated but not fully explained. Here, the influence of an integral cyclic carbonate functional group on (meth)acrylate photopolymerization kinetics is examined in detail with respect to monomers with a wide variety of alternative secondary functionality structure as well as in comparison to conventional mono-and di-(meth)acrylates. The kinetic results from full cure studies of several cyclic carbonate-containing monomers clearly highlight specific structural variations that effectively promote monomer reactivity. Copolymerizations with tetrahydrofurfuryl methacrylate reflect similar dramatic kinetic effects associated with the novel monomers while partial cure homopolymerization studies reveal exceptional dark cure behavior linked to observations of uncommonly low ratios of termination to propagation rates throughout the conversion profile. Temperature effects on reaction kinetics, including both reaction rate and the individual kinetic parameters, as well as the temperature dependence of hydrogen bonding interactions specifically involving the secondary functional groups are probed as a means to understand better the fundamentally interesting and practically important behavior of these monomers.

Dental Materials, May 1, 2014

Dental Materials, Nov 1, 2016

Objective-To assess the influence of hydrophilicity of reactive nanogels on the mechanical perfor... more Objective-To assess the influence of hydrophilicity of reactive nanogels on the mechanical performance of dental adhesives and microtensile bond strength (μTBS) to dentin after 24 h or 3 months of aging. Methods-A series of three nanogels were synthesized: NG1-IBMA/UDMA; NG2-HEMA/ BisGMA; NG3-HEMA/TE-EGDMA. The nanogels were dispersed in solvent, HEMA or BisGMA/HEMA. The degree of conversion (DC) of the materials was measured and the flexural modulus of these polymers was evaluated in dry or wet conditions. For μTBS analysis, a model adhesive was used without nanogel (control) or with the incorporation of nanogels. μTBS was evaluated after storage in distilled water for 24h or 3 months. The analysis of the fracture was performed after μTBS testing. Data were analyzed using ANOVA and Tukey's test (α = 0.05). Results-Water significantly increased the modulus of NG1 and NG2 dispersed in solvent, while significantly decreased the stiffness of NG3. All polymers dispersed in HEMA and Bis-GMA/ HEMA had significantly lower modulus when stored in water. NG2 showed the highest DC in solvent and BisGMA/HEMA. In HEMA, NG1 and NG3 produced the highest DC. After three months, NG2 showed the best μTBS. The μTBS of NG2-containing adhesive resin significantly increased after 3 months, while storage had no effect in the control group, NG1 and NG3. Significance-The more hydrophobic IBMA/UDMA nanogel showed higher bulk material mechanical property results, but the best dentin bond strength values, and notably strength values that improved upon storage, were obtained with the amphiphilic nanogel based on BisGMA/ HEMA.

Macromolecules, Mar 13, 2009

A cyclic acetal-functionalized urethane acrylate monomer is synthesized here and polymerized in a... more A cyclic acetal-functionalized urethane acrylate monomer is synthesized here and polymerized in a crystalline state without the polymerization kinetics being deleteriously affected by the solid state. Depending on the processing conditions, the cyclic acetal urethane acrylate monomer exists in either a metastable liquid state or a crystalline state at ambient conditions. Due to mobility restrictions, extremely poor polymerization kinetics and functional group conversions are typically achieved in solid state polymerizations. However, the solid-state photopolymerization of a cyclic acetal urethane acrylate results in nearly identical polymerization rates and ultimately higher conversion in the crystalline state than in the liquid state under otherwise identical conditions. We conclude that the crystallization process occurs in such a manner as to template the acrylic double bonds in a structure that facilitates rapid, minimally activated propagation.

Soft Matter, 2015

We present a strategy for directly and efficiently polymerizing aqueous dispersions of reactive n... more We present a strategy for directly and efficiently polymerizing aqueous dispersions of reactive nanogels into covalently crosslinked polymer networks with properties that are determined by the initial chemical and physical nanogel structure. This technique can extend the range of achievable properties and architectures for networks formed in solution, particularly in water where monomer selection for direct polymerization and the final network properties are quite limited. Nanogels were initially obtained from a solution polymerization of a hydrophilic monomethacrylate and either a hydrophilic PEG-based dimethacrylate or a more hydrophobic urethane dimethacrylate, which produced globular particles with diameters of 10-15 nm with remarkably low polydispersity in some cases. Networks derived from a single type of nanogel or a blend of nanogels with different chemistries when dispersed in water gelled within minutes when exposed to low intensity UV light. Modifying the nanogel structure changes both covalent and noncovalent secondary interactions in the crosslinked networks and reveals critical design criteria for the development of networks from highly internally branched, nanoscale prepolymer precursors. Supporting Information Supporting Information Available: DLS of EHEMA-PEG550DMA nanogels, GPC analysis of nanogel formation as a function of time, 1 H NMR spectrum of EHEMA-UDMA nanogels, real time conversion via FTIR of networks formed from EHEMA-TTEGDMA nanogels, frequency sweeps of 50 wt% nanogel dispersions, and glass transition behavior of UDMA, TTEGDMA, PEG550DMA, and PEG750DMA homopolymers.

Polymer, Jul 1, 2015

Polymerization-induced phase separation (PIPS) was studied in ambient photopolymerizations of tri... more Polymerization-induced phase separation (PIPS) was studied in ambient photopolymerizations of triethylene glycol dimethacrylate (TEGDMA) modified by poly(methyl methacrylate) (PMMA). The molecular weight of PMMA and the rate of network formation (through incident UVirradiation) were varied to influence both the promotion of phase separation through increases in overall free energy, as well as the extent to which phase development occurs during polymerization through diffusion prior to network gelation. The overall free energy of the polymerizing system increases with PMMA molecular weight, such that PIPS is promoted thermodynamically at low loading levels (5 wt%) of a higher molecular weight PMMA (120 kDa), while a higher loading level (20 wt%) is needed to induce PIPS with lower PMMA molecular weight (11 kDa), and phase separation was not promoted at any loading level tested of the lowest molecular weight PMMA (1 kDa). Due to these differences in overall free energy, systems modified by PMMA (11 kDa) underwent phase separation via Nucleation and Growth, and systems modified by PMMA (120 kDa), followed the Spinodal Decomposition mechanism. Despite differences in phase structure, all materials form a continuous phase rich in TEGDMA homopolymer. At high irradiation intensity (I o =20mW/cm 2 ), the rate of network formation prohibited significant phase separation, even when thermodynamically preferred. A staged curing approach, which utilizes low intensity irradiation (I o =300µW/cm 2 ) for the first ~50% of reaction to allow phase separation via diffusion, followed by a high intensity flood-cure to achieve a high degree of conversion, was employed to form phase-separated networks with reduced polymerization stress yet equivalent final conversion and modulus.