Mechanics of contact and adhesion between viscoelastic spheres: An analysis of hysteresis during loading and unloading

Detailed finite element simulations are carried out to study the adhesive contact of viscoelastic spheres. The spheres are brought into contact by a compressive force that increases at a constant rate. Upon reaching a maximum load, the spheres are unloaded until they separate. We studied in detail the effect of loading and unloading rates on hysteresis and on the pull‐off force for a standard viscoelastic solid. The surface interaction is modeled by the Dugdale–Barenblatt model. Numerical results are compared with analytical models for bonding and debonding, including a recent theory proposed by Johnson. There is excellent agreement between analytical and finite element results for the bonding phase. However, for the debonding phase, current analytical models break down unless the loading and unloading rates are slow in comparison with the material relaxation time. Based on the finite element results, a simple approximate analytical model is proposed to quantify adhesive contact in the debonding phase. We also examine the dependence of hysteresis on interfacial parameters such as the cohesive strength and the intrinsic work of adhesion. Our results show that viscoelastic adhesive contact depends on the details of the surface interaction and cannot be determined solely by the work of adhesion. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 772–793, 2002     

Molecular dynamics study of polymeric chemical gels: Effect of persistence length and crosslinker density

Using molecular dynamics, we study the formation of chemical gels from an initial solution of reactive polymers that undergo a crosslinking reaction. We study the effect of the polymer persistence length and different densities of crosslinkers along the chains. As the reaction progresses, different structural features are identified in the system leading to the development of a percolated cluster. These features are (a) single strands, (b) double strands, and (c) bridges. We found that the total numbers of these three kinds of features are roughly independent of the persistence length; however, the average lengths of single and double strands grow with this variable. The average length of double strands strongly increases with increasing crosslinker density and the amount of single strands sharply falls as crosslinker density grows. We also found that general structural features of polymer networks are highly dependent on chain persistence length and crosslinker density. Fully flexible chains with high density of crosslinkers result in inhomogeneous network structures with large voids. In contrast, precursor chains with high rigidity and scarce number of crosslinkers result in homogeneous networks having small cavities. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1343–1350     

Hydrophilic,cationic large‐core star polymers and polymer networks: Synthesis and physicochemical characterization

Group transfer polymerization was used to prepare hydrophilic, cationic large‐core star polymers (LCSPs) and networks of 2‐(dimethylamino)ethyl methacrylate (DMAEMA) and ethylene glycol dimethacrylate (EGDMA) in a two‐step procedure involving the synthesis of linear DMAEMA arms, followed by their crosslinking using a mixture of DMAEMA monomer and EGDMA crosslinker. The degree of polymerization of the linear chains prepared in the first step was kept constant, while the composition of the crosslinking mixture was varied systematically at a constant amount of crosslinker. The monomer/crosslinker molar ratio determined whether LCSPs or polymer networks would be produced. In particular, a high monomer/crosslinker molar ratio led to the formation of networks, whereas LCSPs were formed when a low monomer/crosslinker molar ratio was used. The absolute weight‐average molecular weight of the LCSPs was determined using static light scattering, whereas their hydrodynamic radii and radii of gyration were determined using dynamic light scattering and small‐angle neutron scattering, respectively. The sol fraction extracted from the networks decreased as the monomer/crosslinker molar ratio increased. The degrees of swelling of all of the networks were measured as a function of pH and were found to increase below pH 7. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3958–3969, 2008     

Phase state effect on adhesion behavior of self-assembled monolayers

The effect of phase state of self-assembled monolayers (SAMs) on adhesion behavior was studied using a combination of atomic force microscopy (AFM) and Johnson-Kendall-Roberts (JKR) methods. The phase state of SAMs was controlled by adjusting the reaction temperature. Order-to-disorder structural transitions in monolayers of n-alkyltrichlorosilanes resulted in dramatic increases in adhesion force and adhesion hysteresis, which represents the first report of alterations in adhesion properties due to phase changes of monolayers without any effect of chain length and surface heterogeneity. This increase in mechanical deformation of the disordered monolayer is understood to be caused by increases in (1) molecular contact between the AFM tip and a disordered monolayer due to the more deformable state of the latter and (2) monolayer deformation during unloading by the JKR probe lens. Adhesion hysteresis was found to have greater sensitivity toward the unloading rate for disordered monolayers. The occurrence of maximum hysteresis at faster rates proves that monolayer chain mobility increases with structural disorder, resulting in increased mechanical deformation.     

A novel crosslinker for UV copolymerization of N-vinyl pyrrolidone and methacrylates to give hydrogels

Methacryloxyethyl vinyl carbonate, a novel crosslinker containing a vinyl carbonate and a methacrylate group which is capable of copolymerizing N-vinyl pyrrolidone and methacrylates, was prepared. With this crosslinker, N-vinyl pyrrolidone (NVP) and methacrylates can copolymerize efficiently under strictly UV conditions. It was found that this crosslinker was able to give hydrogels with higher water content, higher tear strength, and lower modulus, compared to a traditional dimethacrylate crosslinker. In addition, hydrogel lenses fabricated by UV curing of formulations using this crosslinker were found to be superior to those fabricated with established process in terms of optical quality. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1039–1046, 1997     

Biodegradable thermoset shape‐memory polymer developed from poly(β‐amino ester) networks

The purpose of this study was to develop a degradable thermoset shape‐memory polymer from poly(β‐amino ester) (PBAE) networks. PBAE was chosen to be the crosslinker as it is biodegradable and has been projected as a potential material for biomedical applications. The low glass transition temperature of PBAE was increased to a biomedically relevant range using methyl methacrylate and methyl acrylate as the linear chain builders. The thermo‐mechanical properties of the networks were tailored such that they exhibited onset of glass transition temperature in between the room temperature (22 °C) and the body temperature (37 °C). Free‐strain recovery tests under heating and isothermal conditions were performed to quantify shape‐memory behavior. Testing showed that sampled programmed at 10 °C initiated deformation recovery at a lower temperature and a faster rate as compared to programming at 60 °C. Higher thermal conductivity of water enabled the samples to recover faster in water than in air. Samples with higher PBAE crosslinking densities exhibited higher normalized mass loss under regular and accelerated conditions. The amount of water absorption in the networks also increased with the crosslinker concentration independent of the testing conditions. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Formation of elastomeric network polymers from ambient heterogeneous hydrosilations of carboranylenesiloxane and branched siloxane monomers

The Karstedt catalyst‐catalyzed ambient‐condition hydrosilation reactions in hexane of a monomeric vinyl‐containing carboranylenesiloxane, 1 , and three‐branched siloxane crosslinker monomers were discovered to produce elastomeric network polymers at very rapid rates of formation. The flexible and transparent films of the saturated elastomeric network polymers were observed to possess low glass‐transition temperatures (below ?35 °C). Similar hydrosilation reactions at two different reactant ratios involving a diethynyl‐containing carboranylenesiloxane, 2 , and the siloxane crosslinkers produced partially hydrosilated and completely hydrosilated polymeric networked systems, which were transparent and elastomeric at room temperature. The glass‐transition temperatures of all the polymeric systems formulated from 2 were below 0 °C. The elastomeric polymeric networks from 1 and 2 were found to have degradation temperatures in the range of 500–550 °C. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 147–155, 2006     

Application of the JKR Method to the Measurement of Adhesion to Langmuir-Blodgett Cellulose Surfaces

The JKR method has been applied for studying adhesion between poly(dimethylsiloxane) (PDMS) caps and Langmuir–Blodgett cellulose surfaces including the substrate, hydrophobized mica, and two flat mineral surfaces, bare mica and glass. The self-adhesion of PDMS caps and oxidized PDMS caps are included as a reference to compare with literature data. The results of the measurements have been compared with previous studies using the surface force apparatus and similar systems. A satisfactory agreement is obtained for simple systems showing no, or very limited, hysteresis between loading and unloading curves. In several cases, however, a large hysteresis is found between loading and unloading curves, with a larger adhesion measured from the pull-off force than from the JKR-curve determined on loading. This is, for instance, the case for PDMS against cellulose. The situation is analogous to that found in wetting studies showing a large hysteresis between advancing and receding contact angles.     

Degradable polymer networks and star polymers based on mixtures of two cleavable dimethacrylate crosslinkers: Synthesis,characterization, and degradation

Mixtures of two cleavable dimethacrylate crosslinkers, the hydrolyzable di(methacryloyloxy‐1‐ethoxy)methane (DMOEM) and the thermolyzable 1,1‐ethylenediol dimethacrylate (EDDMA), were used for the preparation of neat crosslinker polymer networks, randomly crosslinked polymer networks of methyl methacrylate (MMA), and star polymers of MMA, using group transfer polymerization in tetrahydrofuran (THF). All star polymers and randomly crosslinked polymer networks containing mixtures of the hydrolyzable DMOEM and the thermolyzable EDDMA crosslinkers gave THF‐soluble final products when subjected to sequential thermolysis and hydrolysis, in this order. When applying sequential hydrolysis and thermolysis, only the star polymers with an EDDMA crosslinker content equal to or higher than 50% gave THF‐soluble final products. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5853–5870, 2009     

Gel formation in atom transfer radical polymerization of 2‐(N,N‐dimethylamino)ethyl methacrylate and ethylene glycol dimethacrylate

Copolymers of 2‐(N,N‐dimethylamino)ethyl methacrylate (DMAEMA) and ethylene glycol dimethacrylate (EGDMA) were synthesized via atom transfer radical polymerization using ethyl 2‐bromoisobutyrate as the initiator, Cu(I)Br as the catalyst, and 1,1,4,7,10,10‐hexamethyltriethylene tetramine as the ligand. At low crosslinker levels, the polymerizations followed the first‐order kinetics. However, when the crosslinker level was above 10 mol %, the ln([M]₀/[M]) versus time curves showed deceleration at medium conversions because of the higher reactivity of EGDMA than that of DMAEMA. An acceleration at high conversions was also observed and probably caused by the diffusion limitations of catalyst/ligand complex in the polymer network. The hydrogels were characterized by swelling experiments, and the sol polymers were characterized by the size exclusion chromatographic technique to determine the number‐average molecular weight and polydispersity. The gel data were analyzed and, via a comparison to Flory's gelation theory, found to be more homogeneous than similar hydrogels prepared by conventional free‐radical polymerization methods. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3780–3788, 2001     

Sequential interpenetrating poly(ethylene glycol) hydrogels prepared by UV‐initiated thiol–ene coupling chemistry

Poly(ethylene glycol) (PEG)‐diallyls, ranging from 2 to 8 kDa, were successfully reacted with a trifunctional thiol crosslinker via thiol–ene coupling reaction to construct four different primary PEG hydrogels. These systems were used as scaffolds for the preparation of a library of sequential interpenetrating networks (SeqIPNs). The solid content of the secondary networks varied between 21 and 34% and was dependent on the length of the absorbing PEGs. The gel fractions for the IPNs were above 85%. Additionally, the lowest degree of swelling was found for the IPN based on 2‐kDa PEG (315%), whereas the 8‐kDa PEG IPN exhibited a value of 810%. The SeqIPN strategy facilitated hydrogel systems that cover a larger domain of tensile modulus (192–889 kPa) when compared with single hydrogel networks (175–555 kPa). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis,characterization, and permeability evaluation of hybrid organic–inorganic films

The preparation and characterization of hybrid organic–inorganic films based on poly(dimethylsiloxane), PDMS, crosslinked with nanoclusters obtained from pentaerythrithol triacrylate (PETA) and 2‐aminoethyl‐3‐aminopropyltrimethoxysilane (AS), are reported. The introduction of silica nanoclusters, obtained from tetraethoxysilane as an additional crosslinker, improved the mechanical stability of the films and also produced a noticeable decrease in the solvent sorption and in the distance between the nodes of the polymeric networks. The performance of these films as membranes for gas separation processes was similar to those reported for commercial PDMS, although they presented polar organic PETA/AS crosslinker nuclei. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4281–4292, 2004     

Novel mechanism for the formation of long-chain branching in polyethylene

Polyethylene produced by a vanadium-based polymerization catalyst contains long-chain branching as determined by NMR and rheology, even though the polymer has very low levels of vinyl unsaturation. A new mechanism is proposed for the formation of the long-chain branching, which involves C H bond activation of the polyethylene backbone through a σ-bond metathesis reaction, followed by ethylene insertion at the new V C bond. Consistent with the proposed C H bond activation mechanism, the polymerization catalyst was also found to insert ethylene into the C H bonds of alkanes such as heptane. A bridged metallocene catalyst was also found to activate C H bonds of alkanes suggesting this new mechanism may explain the formation of long-chain branching in some metallocene-produced polyethylene. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2889–2898, 1998     

Poly(methyl methacrylate‐co‐pentaerythritol tetraacrylate‐co‐butyl methacrylate)‐g‐polystyrene: Synthesis and high oil‐absorption property

Well‐defined high oil‐absorption resin was successfully prepared via living radical polymerization on surface of polystyrene resin‐supported N‐chlorosulfonamide group utilizing methyl methacrylate and butyl methacrylate as monomers, ferric trichloride/iminodiacetic acid (FeCl₃/IDA) as catalyst system, pentaerythritol tetraacrylate as crosslinker, and L ‐ascorbic acid as reducing agent. The polymerization proceeded in a “living” polymerization manner as indicated by linearity kinetic plot of the polymerization. Effects of crosslinker, catalyst, macroinitiator, reducing agent on polymerization and absorption property were discussed in detail. The chemical structure of sorbent was determined by FTIR spectrometry. The oil‐absorption resin shows a toluene absorption capacity of 21 g g^?1. The adsorption of oil behaves as pseudo‐first‐order kinetic model rather than pseudo‐second‐order kinetic model. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis of crosslinked poly(butyl methacrylate‐co‐pentaerythritol triacrylate) gel by single electron transfer‐living radical polymerization and its oil‐absorbing properties

A novel high oil‐absorbing crosslinked gel was synthesized by copolymerization of butyl methacrylate (BMA) with a small amount of pentaerythritol triacrylate (PETA) crosslinker using single electron transfer‐living radical polymerization (SET–LRP) initiated with carbon tetrachloride (CCl₄) and catalyzed by Cu(0)/hexamethylenetetramine (HMTA) in N, N‐dimethylformamide (DMF). The polymerization followed first‐order kinetics as indicated by linear increase of monomer concentration with reaction time. Effects of reaction temperature, crosslinker, initiator, and catalyst on the oil‐absorbing properties of the crosslinked gel were investigated in detail. The oil absorptions of the crosslinked gel to chloroform, toluene could reach 51.9, 34.5 g/g, respectively. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Effects of crosslinker density on the polymer network structure in poly‐N,N‐dimethylacrylamide hydrogels

To investigate the effects of crosslinker density on the properties of hydrogels, compression tests, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and Raman measurements were performed on poly‐N,N‐dimethylacrylamide hydrogels. The results of the compression tests showed that the Young's modulus increases as the crosslinker density increases. To understand the mechanism of the change in the mechanical properties, the structures of the polymer networks and water and the molecular vibrations were analyzed using SEM, DSC, and Raman methods. From the SEM images, it was found that the porosity estimated from the mesh size and cell density increases with increasing crosslinker density. In addition, the DSC and Raman results show that the thickness of the bound water increases as the porosity increases, although the density of the polymer chains in the porous wall remains nearly constant. The increase in the number density of polymer chains can be one of the mechanisms contributing to the increase in the mechanical strength of the hydrogels at lower crosslinker density below 5 mol %, as proposed by previous studies. At higher crosslinker density, however, the number density of polymer chains does not increase with increasing crosslinker density. The present results suggest that the bound water plays an important role in strengthening the hydrogel. The water structure may be one of the dominant factors governing the chemical and physical properties of hydrogels. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1017–1027     

Model reactions and formation of epoxy networks with the phenylbenzoate mesogen

The phenylbenzoate mesogen was introduced into epoxy networks by the crosslinker 4-hydroxyphenyl-4-hydroxybenzoate and by the diglycidylether of 4-hydroxyphenyl-4-hydroxybenzoate, respectively. Rigid networks were synthesized on the basis of 4-hydroxyphenyl-4-hydroxybenzoate and the diglycidylether of bisphenol A, and flexible networks were prepared by reaction of the diglycidylether of butanediol-1.4 with the same dihydroxy compound. Model investigations were used to obtain information about the reactivity differences of the phenolic hydroxyl groups of the bisphenol used for network formation. Furthermore, the thermal properties of the main products isolated from the model reactions are strongly influenced by the substituents at the phenylbenzoate structure. Some of these model substances demonstrate structures that can be also found in the networks. In addition, photoinduced cationic crosslinking of the diglycidylether of 4-hydroxyphenyl-4-hydroxybenzoate results in networks with different thermal properties that are dependent on the temperature of network formation. Moreover, the temperature used during crosslinking influences the formation of ordered structures in the networks. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2653–2688, 1997     

Thermoresponsive super water absorbent hydrogels prepared by frontal polymerization of N‐isopropyl acrylamide and 3‐sulfopropyl acrylate potassium salt

Super water absorbent polymer hydrogels were synthesized by frontal polymerization. These materials were obtained by copolymerizing N‐isopropyl acrylamide (NIPAAm) and 3‐sulfopropyl acrylate potassium salt (SPAK) in the presence of N,N′‐methylene‐bis‐acrylamide as a crosslinker. It was found that their swelling behavior in water can be easily tuned by using either the appropriate monomer ratio or the amount of the crosslinker used. Namely, the swelling ratio was found to range from about 1000% for the NIPAAm homopolymer in the presence of 5.0 mol % of crosslinker, up to 35,000% for the sample containing 87.5 mol % of SPAK and 1.0 mol % of crosslinker. The affinity toward water was also confirmed by contact angle analysis. Moreover, the obtained hydrogels exhibit a thermoresponsive behavior, with a lower critical solution temperature of about 28–30 °C. This value is close to that of poly(NIPAAm) but with a swelling capability that dramatically increases as the amount of SPAK increases. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Interfacial friction of thin PDMS network films

This study focuses on developing dry, surface‐tethered polymeric lubricant coatings capable of significantly decreasing friction and wear of nano‐ and micrometer scale machines. Vinyl‐terminated polydimethylsiloxane chains are spin‐coated with a crosslinking agent and platinum catalyst onto silicon wafers functionalized with a self‐assembling monolayer containing reactive vinyl groups. Lateral force microscopy (LFM) measurements employing a bead probe are used to quantify the coefficient of friction (COF) and adhesion characteristics of the PDMS‐SAM surface tethered networks. The combined polymer network and SAM layer manifest extremely low friction coefficients, μ = 4 × 10^?3, which is nearly one order of magnitude lower than the friction coefficient of the bare silicon substrate. The lowest friction forces are measured using silicon substrates covered with nanometer thick, peroxide crosslinked PDMS networks; though poorly crosslinked, these networks display COFs as much as ten‐times lower than a solitary SAM coating layer. Micrometer thick end‐linked optimal networks also manifest attractive interfacial friction properties, with COFs approximately three times larger than the thinner, imperfect networks. These observations are discussed in terms of the structure of the polymer networks and the role of adhesion forces on interfacial friction. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1773–1787, 2008     

Autoacceleration and inhibition: Free volume. Epoxy-amine kinetics

The epoxy-diamine cure process was studied. We found that the mechanism can be described in three steps: (i) initiation up to 20–25% of conversion. (ii) autoacceleration and (iii) inhibition. It has been observed that after the initiation there is a clear autoacceleration effect which has been explained in terms of free volume, considerations: the volume occupied by the products of reaction diminishes the available volume increasing the “local concentration” of the reactants and therefore the rate of reaction. The reaction was followed by FTIR (near infrared) as the main technique. We used a purified epoxy resin as well as phenyl glycidyl ether cured with m-xylenediamine. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1001–1016, 1998