Pressure-sensitive Adhesives Research Articles

Revealing the coaction of viscous and multistability hysteresis in an adhesive, nominally flat punch: A combined numerical and experimental study

Viscoelasticity is well known to cause significant hysteresis of crack closure and opening when an elastomer is brought in and out of contact with a flat, rigid, adhesive counterface. A separate origin of adhesive hysteresis is small-scale, elastic multistability. Here, we study a system in which both mechanisms act concurrently. Specifically, we compare the simulated and experimentally measured time evolution of the interfacial force and the real contact area between a soft elastomer and a rigid, flat punch, to which small-scale, single-sinusoidal roughness is added. To this end, we further the Green’s function molecular dynamics method and extend recently developed imaging techniques to elucidate the rate- and preload-dependence of the pull-off process. Our results reveal that hysteresis is much enhanced when the saddle points of the topography come into contact, which, however, is impeded by viscoelastic forces and may require sufficiently large preloads. A similar coaction of viscous- and multistability effects is expected to occur in macroscopic polymer contacts and to be relevant, e.g., for pressure-sensitive adhesives and modern adhesive gripping devices.

Mechanistic insights into the effect of drug content on adhesive properties of transdermal patch containing lidocaine

This study aims to shed light on the relationship between drug content and adhesive properties in drug-in-adhesive transdermal patch, and to elucidate molecular mechanisms from the perspective of polymer chain mobility. Lidocaine was selected as model drug. Two acrylate pressure sensitive adhesives (PSAs) with different polymer chain mobility were synthesized. Tack adhesion, shear adhesion and peel adhesion of PSAs with 0, 5%, 10%, 15% and 20% w/w lidocaine contents were tested. Polymer chain mobility was determined by rheology and modulated differential scanning calorimetry experiments. Drug-PSA interaction was analyzed by FT-IR. The effect of drug content on free volume of PSA were determined by positron annihilation lifetime spectroscopy and molecular dynamics simulation. It was found that the polymer chain mobility of PSA was increased with increasing drug content. Due to the variation of polymer chain mobility, tack adhesion increased, and shear adhesion decreased. It was proved that interactions between polymer chains were destroyed by drug-PSA interactions, free volume between polymer chains was expanded, resulting in the increase of polymer chain mobility. We can conclude that the effect of drug content on polymer chain mobility should be considered, when designing a transdermal drug delivery system with controlled and satisfactory adhesion.

Study of Applying Naturally Occurring Mineral Materials for Silicone Pressure-Sensitive Adhesives

Silicones are commonly used as adhesives when high-quality materials are required due to harsh environmental conditions such as high temperature, humidity, etc. To ensure high resistance to environmental conditions, including high temperatures, modifications of silicone adhesives are made using fillers. The characteristics of a modified silicone-based pressure-sensitive adhesive with filler are the focus of this work. Functionalized palygorskite was prepared in this investigation by grafting 3-mercaptopropyltrimethoxysilane (MPTMS) onto palygorskite (palygorskite-MPTMS). The palygorskite was functionalized using MPTMS under dried conditions. FTIR/ATR spectroscopy, thermogravimetric analysis, and elemental analysis were all used to characterize the obtained palygorskite-MPTMS. MPTMS loading onto palygorskite was also proposed. The results demonstrated that palygorskite's initial calcination favors the grafting of functional groups on its surface. New self-adhesive tapes based on palygorskite-modified silicone resins have been obtained. This functionalized filler allows for the improvement of the compatibility of palygorskite with specific resins for application in heat-resistant silicone pressure-sensitive adhesives. The new self-adhesive materials showed increased thermal resistance while maintaining good self-adhesive properties.

An Exploratory Study on Determining and Modeling the Creep Behavior of an Acrylic Pressure-Sensitive Adhesive

In the present paper, an exploratory study on the creep behavior of a pressure sensitive adhesive (PSA) is performed. After the determination of the quasi-static behavior of the adhesive for bulk specimens and single lap joints (SLJ), SLJs were subjected to creep tests at 80%, 60%, and 30% of their respective failure load. It was verified that the durability of the joints increases under static creep conditions as the load level decreases, with the second phase of the creep curve becoming more pronounced, where the strain rate is close to zero. In addition, cyclic creep tests were performed for the 30% load level at a frequency of 0.04 Hz. Finally, an analytical model was applied to the experimental results in order to reproduce the values obtained for both static and cyclic tests. The model was found to be effective, reproducing the three phases of the curves which allowed for the characterization of the full creep curve, something not commonly found in the literature, especially for PSAs.

UV-Curable Polyurethane Acrylate Pressure-Sensitive Adhesives with High Optical Clarity for Full Lamination of TFT-LCD

Optically clear pressure-sensitive adhesives (PSAs) face the challenges presented by a range of electronic and touch screen applications. Although many efforts have been made to manipulate the optical and adhesion properties of ultraviolet (UV)-curable acrylate-based PSAs, further application and large-scale production are still limited owing to the intrinsically poor processability that stems from the large content of the high-vinyl-equivalent and low-viscosity acrylic monomers. Introducing a low-vinyl-equivalent and high-viscosity polyurethane acrylate (PUA) prepolymer into the formulation is a facile method to solve this issue without sacrificing the transparency. In this study, a series of PUA prepolymers are prepared to construct the model of PUA-co-2-ethylhexyl acrylate (2EHA), denoted as poly(PUA-2EHA). The influence of PUA prepolymer architectures (average functionality and molecular features) on the optical and adhesion properties is elaborately discussed. The chemical cross-linking-induced enhancement of the haze values of PUA-based PSAs is investigated for the first time. Moreover, an improved and uniform bright image display without blemish, which is usually called the Mura defect-free image display in the industrial field, is obtained by using poly(PUA-2EHA) as the optically clear adhesive for full lamination of the thin-film transistor liquid crystal display (TFT-LCD) module. The laminated TFT-LCD module could be disassembled easily without leaving the residue on the screen. These results provide clear design guidelines to regulate the properties of PUA-based PSAs, which are especially valuable for the large-scale industrial production of UV-cured PSAs and facilitate the development of display technologies.

Formulation Development and Molecular Mechanism Characterization of Long-Acting Patches of Asenapine for Efficient Delivery by Combining API-ILs Strategy and Controlled-Release Polymers

The objective of our study, which combined API-ILs strategy and controlled-release polymers, was to prepare a 72 h long-acting drug-in-adhesive patch for optimum delivery of asenapine (ASE). Special attention was paid to the permeation promotion mechanism and the controlled release behavior of ASE-ILs in pressure sensitive adhesives (PSA). Formulation factors were investigated by ex vivo transdermal experiments. The optimized patch was evaluated by pharmacokinetics study and skin irritation test. The obtained formulation was as follows, 15% w/w ASE-MA (about 1136 μg/cm2 ASE, 413 μg/cm2 MA), AACONH2 (Amide adhesive) as the matrix, 80 μm thickness, backing film of CoTran™ 9733. The optimized patch displayed satisfactory ex vivo and in vivo performance with Q 72 h of 620 ± 44 µg/cm2 and Fabs of 62.4%, which utilization rate (54.6%) was significantly higher than the control group (38.3%). By using the classical shake flask method, 13C NMR, DSC, and FTIR, the physicochemical properties and structure of ILs were characterized. log Do/w, ATR-FTIR, Raman, and molecular dynamics simulation results confirmed that ASE-MA (MA: 3-Methoxypropionic acid) had appropriate lipophilicity, and affected lipid fluidity as well as the conformation of keratin to improve the skin permeation. The FTIR, MDSC, rheology, and molecular docking results revealed that hydrogen bond (H-bond), were formed between ASE-MA and PSA, and the drug increased the molecular mobility of polymer chains. In summary, the 72 h long-acting patch of ASE was successfully prepared and it supplied a reference for the design of long-acting patches with ASE.

Synthesis and Properties of a Novel Thermally Conductive Pressure-Sensitive Adhesive with UV-Responsive Peelability.

Thermally conductive pressure-sensitive adhesive (PSA) has received a great amount of attention in recent years, but the traditional PSA hardly loses adhesion properties after UV irradiation or heating. Therefore, endowing thermally conductive adhesive with UV-responsive peelability becomes a design strategy. Herein, vinyl-functionalized graphene (AA-GMA-G) is prepared by modifying graphene with acrylic acid and subsequently reacting with glycidyl methacrylate. Then, the UV-curable acrylate copolymer is synthesized by grafting glycidyl methacrylate. Finally, the novel thermally conductivity PSA with UV-responsive peelability is obtained by blending the copolymer with AA-GMA-G and photoinitiator. The results show that the PSA at 2wt% AA-GMA-G loading exhibits an excellent thermal conductivity (0.74Wm-1 K-1 ) and a relatively strong peel strength, increasing by 15% compared with pristine graphene/PSA. Interestingly, the peel strength of AA-GMA-G/PSA can achieve a dramatic drop after UV treatment, and the decrease rate is 96.7%. Therefore, the novel thermally conductive PSA with UV-responsive peelability has potential applications in certain electronic devices.

Press-N-Go On-Skin Sensor with High Interfacial Toughness for Continuous Healthcare Monitoring.

On-skin electronic sensors are demanded for healthcare monitoring such as the continuous recording of biopotential and motion signals from patients. However, the mechanical mismatches and poor interface adhesion at the skin/sensor interfaces always cause high interfacial impedance and artifacts, frequent interfacial failure, and unexpected depletion of the device, which significantly limit the performance of the sensors. We here develop an on-skin sensor based on a conductive pressure-sensitive tape, which is assembled from supramolecular dual-cross-linked hydrogel composites. Both covalent and noncovalent cross-links in the hydrogel networks could harvest high flexibility, pressure-sensitive adhesion, and high interfacial toughness altogether, enabling a convenient "Press-N-Go" application of the sensor on human skin without additional pre/post-treatment on the skin or the senor. The high conformability and low resistivity of the tape can sustainably lower the interfacial impedance and thus improve signal quality in various measurement conditions. Our design provides a feasible path to develop interface-toughened on-skin electronics, which is desired in dynamic human-machine interfaces.

Flexible and Robust Triboelectric Nanogenerators with Chemically Prepared Metal Electrodes and a Plastic Contact Interface Based on Low-Cost Pressure-Sensitive Adhesive.

Triboelectric nanogenerators (TENGs) are devices that can harvest energy from mechanical motions; such devices can be used to power wearable sensors and various low-power electronics. To increase the lifetime of the device, scientists mainly use the method of making TENG in a hard skeleton to simplify the complex possible relative movements between two triboelectric parts. However, the hard skeletons cannot be embedded in soft and lightweight clothing. To make matters worse, the materials used in the garments must be able to withstand high mechanical forces when worn, such as the pressure of more than 100 KPa exerted by body pressure or everyday knocks. Notably, the TENGs are usually made of fragile materials, such as vacuum-evaporated metal electrodes and nano-sized coatings, on the contact interface; these electrodes and coatings often chip or wear off under the action of external loads. In this work, we succeeded in creating a thin, light-weight, but extremely robust garment-integrated triboelectric nanogenerator (G-TENG) that can be embedded in clothing and pass the water wash test. First, we chemically deposited a durable electrode with flexible properties for G-TENG using a novel technique called polymer-assisted metal deposition (PAMD). The as-formed metal electrodes are firmly bonded to the plastic substrate by a sub-10 nm adhesive polymer brush and can withstand a pressure of 22.5 MPa and a tear force of 0.7 MPa. We then removed the traditionally used fragile nanoparticle materials and the non-durable poly-dimethylsiloxane (PDMS) layer at the triboelectric interface, and then used a cost-effective, durable and slightly flowable pressure-sensitive adhesive to form a plastic contact interface. Such a soft plastic interface can ensure full contact of the triboelectric materials, which is excellent in complex environments and ultimately improves the power generation efficiency of the devices. The as-formed low-cost energy harvesting device could become an industry standard for future smart clothing.

Sticky Architecture: Encoding Pressure Sensitive Adhesion in Polymer Networks.

Pressure sensitive adhesives (PSAs) are ubiquitous materials within a spectrum that span from office supplies to biomedical devices. Currently, the ability of PSAs to meet the needs of these diverse applications relies on trial-and-error mixing of assorted chemicals and polymers, which inherently entails property imprecision and variance over time due to component migration and leaching. Herein, we develop a precise additive-free PSA design platform that predictably leverages polymer network architecture to empower comprehensive control over adhesive performance. Utilizing the chemical universality of brush-like elastomers, we encode work of adhesion ranging 5 orders of magnitude with a single polymer chemistry by coordinating brush architectural parameters-side chain length and grafting density. Lessons from this design-by-architecture approach are essential for future implementation of AI machinery in molecular engineering of both cured and thermoplastic PSAs incorporated into everyday use.

Influence of Acid-Modified Clinoptilolite on the Self-Adhesive Properties of Silicone Pressure-Sensitive Adhesives.

The preparation of a new "eternally alive adhesive" based on silicone pressure-sensitive adhesives with clinoptilolite is presented. Neat and acid-modified (i.e., treated with sulfuric acid (VI)) clinoptilolite was used. The effect of clinoptilolite acid treatment on the adhesive properties of pressure-sensitive adhesive tapes was tested. The obtained tapes exhibited increased thermal resistance when compared to the reference tapes. Despite introducing the filler, the pressure-sensitive adhesive tapes maintained good functional properties. The new self-adhesive materials show promising implementation potential where increased thermal resistance is required.

Asphaltene-Stabilized Polyisobutylene Pressure-Sensitive Adhesives for Ultraviolet Protection and Surface Bonding.

The usual way to protect indoor areas from solar UV radiation is to use UV-absorbing materials, which are applied as a thin film on the surface of the windowpane. Asphaltenes are useless wastes from crude oil refining that absorb UV radiation well, which gave the idea of their use in protective coatings. Pressure-sensitive adhesives based on polyisobutylene containing from 5 to 30 wt% of asphaltenes were obtained. Deterioration of the adhesive properties with the introduction of 5-20 wt% of asphaltenes was shown by adhesion tests, which can be associated with the plasticization of the polymer matrix. At the same time, the use of 30 wt% of asphaltenes leads to the polymer matrix reinforcement with the restoration of adhesive properties to the original level or even slightly higher. The rheological study of adhesives at 25 °C and 120 °C showed the structural network formation by asphaltenes at a content of 30 wt%, explaining the increase in adhesion performance. According to microscopy, asphaltenes are flat brown glass shards in a polymer matrix. They absorb electromagnetic radiation, predominantly in the UV range, while maintaining relative translucency in the visible range. This makes it possible to obtain thin films from the asphaltene-filled adhesive for bonding glass sheets to produce UV-blocked and tinted windowpanes.

Diffusiophoresis-Driven Stratification in Pressure-Sensitive Adhesive Films from Bimodal Waterborne Colloids.

The uses of pressure-sensitive adhesives (PSAs) are wide ranging, with applications including labels, tapes, and graphics. To achieve good adhesion, a PSA must exhibit a balance of viscous and elastic properties. Previous research has found that a thin, elastic surface layer on top of a softer, dissipative layer resulted in greater tack adhesion compared with the single layers. Superior properties were achieved through a bilayer obtained via successive depositions, which consume energy and time. To achieve a multilayered structure via a single deposition process, we have stratified mixtures of waterborne colloidal polymer particles with two different sizes: large poly(acrylate) adhesive particles (ca. 660 nm in diameter) and small poly(butyl acrylate) (pBA) particles (ca. 100 nm). We used two types of pBA within the particles: either viscoelastic pBA without an added cross-linker or elastic pBA with a fully cross-linked network. Stratified surface layers of deuterium-labeled pBA particles with thicknesses of at least 1 μm were found via elastic recoil detection and qualitatively verified via the analysis of surface topography. The extent of stratification increased with the evaporation rate; films that were dried slowest exhibited no stratification. This result is consistent with a model of diffusiophoresis. When the elastic, cross-linked pBA particles were stratified at the surface, the tack adhesion properties made a transition from brittle failure to tacky. For pBA without an added cross-linker, all adhesives showed fibrillation during debonding, but the extent of fibrillation increased when the films were stratified. These results demonstrate that the PSA structure can be controlled through the processing conditions to achieve enhanced properties. This research will aid the future development of layered or graded single-deposition PSAs with designed adhesive properties.

Influence of UV on the self-adhesive properties of silicone pressure-sensitive adhesives

The paper presents the results of research on the UV radiation influence on the self-adhesive properties of silicone adhesives. The adhesives were obtained by cross-linking commercial resins (PSA 590, Q2-7566) at the temperature of 110°C, using different amounts (0–3 wt%) of bis(2,4-dichlorobenzoyl) peroxide. Self-adhesive properties of adhesives such as adhesion, tack, and durability before and after aging were determined. The adhesives showed stable self-adhesive properties, however, the PSA 590 adhesive had a higher maximum operating temperature than the Q2-7566 adhesive.

Organophilized Montmorillonites as Fillers for Silicone Pressure-Sensitive Adhesives.

In the presented work, organophilized montmorillonites (OMMT) with selected quaternary ammonium compounds (QAC) with different chemical structure ((trioctylmethylammonium chloride-A336, dimethyloctadecyl[3-trimethoxysilyl)propyl]ammonium chloride-D, cetyltrimethylammonium bromide-CTAB, 2-methacryloxyethyltrimethylammonium chloride-MOA) were obtained and used as fillers for physically modified silicone pressure-sensitive adhesives (Si-PSA). Before OMMT addition into Si-PSA matrix, they were analyzed via TGA and XRD techniques. Type of chemical structure of QAC affected d-spacing of OMMT. New self-adhesive materials were obtained based on prepared Si-PSA compositions by adding the obtained fillers to the polymer matrix. New tapes exhibit a good level of useful properties as adhesion, cohesion, and tack-the values did not change or slightly decreased; in addition, the tapes with addition of OMMT showed high thermal resistance reaching the measuring limit of the test equipment-to 225 °C.

Preparation and drug release performance of amphiphilic medical hot‐melt pressure sensitive adhesives based on polystyrene‐isoprene‐styrene

AbstractHot‐melt pressure‐sensitive adhesives (HMPSAs) with polystyrene‐isoprene‐styrene (SIS) as the backbone material are widely used in transdermal drug delivery systems (TDDS) because of their high cohesive strength and drug‐carrying capacity. However, it is restricted by its high hydrophobicity when loaded with hydrophilic drugs. In this study, HMPSAs with amphiphilic properties were created by mixing SIS with fatty alcohol polyoxyethylene ether (AEO‐9) and polyethylene glycol (PEG) of different molecular weights to improve the ability of HMPSAs to deliver hydrophilic drugs. The effects of different molecular weights of PEG on the hydrophilicity of HMPSAs were also investigated. Additionally, gardenia glycosides and oleanolic acid were selected for drug release experiments. Compared to untreated HMPSAs, HMPSAs modified with AEO‐9 and PEG2000 could convert from hydrophobic to hydrophilic. The contact angle could be reduced from 91.8 to 25.6°, and the 24‐hour water absorption could be raised by 170%. The drug release experiments demonstrate that SIS/AEO‐9/PEG2000 enhances the release efficiency of the hydrophilic drug gardenia jasminoides by 69%. In summary, as a novel amphiphilic medicinal HMPSAs, SIS/AEO‐9/PEG offered a broad application promise in hydrophilic drug release.

Biomass-sourced polymers for pressure-sensitive adhesive applications

Pressure-sensitive adhesives are self-adhesive chemical products that have gradually supplanted traditional glues in recent years. Most of the commercially available pressure-sensitive adhesives are derived from petrochemical resources. The increasing attention to environmental protection, coupled with the introduction of stringent regulations and rising oil prices, has led to widespread attention being paid to the development of sustainable pressure-sensitive adhesives from biomass sources. This paper summarizes the biomass-sourced pressure-sensitive adhesives and their modification methods that have been reported in recent years as promising alternatives to petrochemical resources.

Preparation and optimization of a lignin-based pressure-sensitive adhesive

D-optimal designs were applied to find the best parameters for the preparation of lignin-based pressure-sensitive adhesives (PSA) for sticky notes. Organosolv lignin was directly incorporated into a polycarboxylate polyether (PCE)/water matrix. The independent variables considered in the experimental design were the ratio between PCE, lignin, and water and the curing parameters. The distance traveled by the ball (tack), the peel-off losses and the final water content were the analyzed responses that allowed the optimization of the PSA formulation. The accuracy, the precision and the efficiency of the model were evaluated during the first experimental design for the formulation of the lignin-based adhesive named DES-OL-ADH. This formulation was optimized during the second experimental design abbreviated DES-OL-OPT. The coefficients of determination of the tack, the peel-off losses and the final water content were 0.98, 0.99 and 0.99, respectively. The model was satisfactory which allows the optimization of the PSA formulation. The DES-OL-OPT suggests that lignin-based PSA can be prepared as a sticky note application with 5 wt% of lignin, 84 wt% of PCE and 11 wt% of added water in the oven at 130 °C for 60 min, which shows a higher tackiness and similar peel-off losses than the commercial sticky notes PSAs.•Protocol optimization for the preparation of a green pressure sensitive adhesive (PSA) from PCE polymer, lignin, and water.•Influence of 5 compositional or processing parameters on adhesive performance through a 2-steps d-optimal experimental design.•Development of a new method, based on peel-off losses, to assess the performance of a PSA.

Hydrophobically modified complex coacervates for designing aqueous pressure-sensitive adhesives.

The rheology of complex coacervates can be elegantly tuned via the design and control of specific non-covalent hydrophobic interactions between the complexed polymer chains. The well-controlled balance between elasticity and energy dissipation makes complex coacervates perfect candidates for pressure-sensitive adhesives (PSAs). In this work, the polyanion poly(3-sulfopropyl methacrylate) (PSPMA) and the polycation quaternized poly(4-vinylpyridine) (QP4VP) were used to prepare complex coacervates in water. Progressive increase of hydrophobicity is introduced to the polyanion via partial deprotection of the protected precursor. Hence, the polymer chains in the complex coacervates can interact via both electrostatic (controlled by the amount of salt) and hydrophobic (controlled by the deprotection degree) interactions. It was observed that: (i) a rheological time-salt-hydrophobicity superposition principle is applicable, and can be used as a predictive tool for rheology, (ii) the slowdown of the stress relaxation dynamics, due to the increase of hydrophobic stickers (lower deprotection degree), can be captured by the sticky-Rouse model, and (iii) the systematic variation of hydrophobic stickers, amount of salt, and molecular weight of the polymers, enables the identification of optimizing parameters to design aqueous PSA systems. The presented results offer new pathways to control the rheology of complex coacervates and their applicability as PSAs.

Understanding the role of crosslink density and linear viscoelasticity on the shear failure of pressure-sensitive-adhesives.

Pressure-sensitive-adhesives (PSAs) are ubiquitous in electronic, automobile, packaging, and biomedical applications due to their ability to stick to numerous surfaces without undergoing chemical reactions. Although these materials date back to the 1850s with the development of surgical tapes based on natural rubber, their resistance to shear loads remains challenging to predict from molecular design. This work investigates the role of crosslink density on the shear resistance of model PSAs based on poly(2-ethylhexyl acrylate-co-acrylic acid) physically crosslinked with aluminum acetylacetonate. The key result is that crosslinking PSAs leads to notable stress concentrations ahead of the peel front, as well as a transition from cohesive to adhesive failure. The shear stress distributions, as evaluated by means of a linearly viscoelastic shear lag model, suggest that this transition is related to the evolution of the ratio of the load transfer length to the bond length as dictated by the mechanical properties of the backing and adhesive layers, and the geometry of the tape.