After cellulose, lignin is the second most abundant natural polymer in the world. It has multiple functional groups, providing great potential for polymer production. In this project, we explored the use of this renewable and valuable resource in two different adhesive applications to displace petroleum-based additives, thereby providing a more sustainable and “green” product. In this regard, two types of lignin, water-soluble (Amalin LPH) and non-water-soluble lignin (Amalin HPH) provided by the British Columbia Research Institute (BCRI) were used. In the first case, lignin was added to a pressure-sensitive adhesive (PSA) formulation via in-situ seeded semi-batch emulsion polymerization. It was seen that lignin does not readily take part in the polymerization reaction; rather, its presence results in reaction inhibition. Therefore, Amalin LPH lignin was modified via acrylation to overcome this issue. In another modification approach, maleic anhydride was used to produce maleated Amalin HPH lignin. Both the acrylated and maleated lignins were used in butyl acrylate/methyl methacrylate emulsion copolymerizations to produce PSA films. A series of controlled experiments with different lignin loadings was conducted. Adhesive properties of the PSA films were measured and compared with the corresponding acrylic base case formulation. The incorporation of lignin in the PSA formulation was a “green” solution to conventional PSA production and led to a simultaneous increase in tack and shear strength. Further characterization of the latex films via transmission electron microscopy (TEM) showed that lignin was successfully incorporated into the polymer particles. It also showed that the use of maleated lignin at a higher concentration led to a core-shell morphology. In the second application, unmodified Amalin LPH lignin was used to create a starch-based adhesive through the Stein-Hall process, a two-step process involving a “carrier” portion and a “slurry” portion. Several formulations with lignin loadings up to 35 wt% distributed in varying ratios in the carrier and slurry portions were prepared. It was shown that the addition of lignin to the starch-based adhesive formulation increases the water-resistance of the adhesive. Therefore, lignin addition is a solution for a common issue in starch-based adhesives, their lack of water-resistance due to the high affinity of starch toward water. Lignin incorporation solely in the slurry portion significantly increased the strength of the glued joints in a paper board adhesive test. The use of lignin as a renewable replacement of petroleum-based components in two different adhesive formulations was demonstrated successfully. This research strongly suggests that lignin can be used as a high value-added property modifier in adhesive applications.

Unexpectedly, it was found that when a waterborne polyacrylate adhesive was placed on carbon steel it was not tacky; this was not the case for the same adhesive placed on stainless steel. It was determined that the surface energy, as measured with liquid contact angles, of the adhesive films is significantly different between the two films, with the non-tacky film having a higher surface energy. Atomic force microscopy (AFM) showed that the non-tacky surface has a higher roughness which minimizes the contacting area between the film and a contacting surface. Analysis of the heating of the carbon steel coupon with infrared thermography shows a non-uniform temperature profile at the surface. This experimental data is corroborated using a 2-D heat transfer model that incorporates the heat transfer characteristics of the various components of carbon steel. Surface driven flow, or Marangoni convection, can develop from temperature gradients and are known to cause increased roughness in polymer films. IR thermography measurements of the adhesive film during drying shows larger temperature differences for the films on carbon steel than on stainless steel. These larger temperature differences induce greater Marangoni convection, which result in the rougher surfaces on carbon steel that were measured with AFM. The effect of lowering the tack of a polyacrylate film has significant impact in the dryer section of a paper machine. This effect was quantified using the Web Adhesion Drying Simulator, which is a laboratory-scale apparatus that measures the energy required to pull the sheet from a metal surface. By substituting the adhesive-on-stainless steel with the less-sticky adhesive-on-carbon steel surface, the energy required to pull the sheet from the metal surface was reduced significantly and the picking associated with the test was nearly eliminated.

Thorough understanding of interfaces requires an assessment of both the surface and bulk properties through the use of multiple techniques. In this thesis, infrared absorption, Raman scattering and sum frequency generation were used as vibrational probes of different features of interfacial systems including the ability to measure surface and bulk effects. Two-dimension correlation analysis was used to study the relationship between the spectral response of the different techniques. Attenuated total reflection absorption, bulk Raman scattering and sum frequency generation were used to study the adsorption of ethanol--water mixture on fused silica. With the use of two-dimension correlation analysis, interesting results were observed concerning the behavior of the surface in respect to the bulk. Surface concentration of ethanol were concluded to be higher than in the bulk indicative of competitive adsorption. Furthermore, at low concentration ethanol was shown to adsorb to the surface in dimers, to then form a bilayer of strongly oriented ethanol molecules at higher concentration. At highest concentration, this bilayer is disturbed, leaving only one layer at the surface of oriented ethanol molecules. The same spectroscopic techniques were applied to pressure sensitive adhesives of different composition while drying on a sapphire surface. The presence or absence of acrylic acid in the material was shown to alter the reorientation at the surface while drying. In the case where no acrylic acid is present, the orientation of the polymer at the surface was driven by the packing of the molecules at the surface. When acrylic acid was present in the pressure sensitive adhesive, reorientation occurred much faster and was caused by strong hydrogen bonding with the surface of the sapphire. An increase in acrylic acid composition, increased the rate of reorientation. An experimental set up was constructed to specifically study interfaces with a nonuniform distribution within the plane of the surface. This allows for concomitant measurement of polarized total internal reflection Raman scattering and sum frequency generation spectroscopy along with bright field imaging and cross polarized imaging. This set up was used to study the L-histidine crystal in situ adsorbed on fused silica. The polarized experiments along with calculations allowed for a more in-depth analysis of the crystal orientation effect on the birefringence, the Raman and the sum frequency generation. / Graduate

d-Limonene (Lim) was used in various polymer formulations to achieve a more sustainable polymerization. Lim is a renewable and essentially non-toxic compound, derived from citrus fruit peels, that may replace some of the many toxic and fossil-based chemicals used in polymer synthesis. Bulk free-radical polymerizations of n-butyl acrylate (BA) with Lim were performed to investigate Lim co-polymerization kinetics and estimate the monomer reactivity ratios, important parameters in the prediction of copolymer composition. Kinetic modeling of the BA/Lim copolymerization was performed with PREDICI simulation software. The model supports the presence of a significant degradative chain transfer reaction due to Lim. This reaction mechanism is due to the presence of allylic hydrogen in Lim. Nonetheless, relatively high molecular weight polymers were produced. It was concluded that Lim behaves more like a chain transfer agent than a co-monomer. Terpolymerizations of BA, butyl methacrylate (BMA) with Lim were then performed. In order to predict the terpolymer composition, the monomer reactivity ratios for BA/BMA were estimated. By applying the three pairs of co-monomer reactivity ratios to the integrated Mayo-Lewis equation, terpolymer compositions were ably predicted up to high monomer conversion levels. Lim was then used as a chain transfer agent to prepare core-shell latex-based pressure sensitive adhesives (PSA) comprising BA and styrene via seeded semi-batch emulsion polymerization. By varying the concentration of Lim and divinylbenzene crosslinker, the core polymer microstructure was modified to yield different molecular weights and degrees of crosslinking. The core latex was then used as a seed to prepare core-shell latexes. By changing the Lim concentration during the shell-stage polymerization, the molecular weight of shell polymer was also modified. The latexes were characterized for their microstructure and were cast as films for PSA performance evaluation. The PSA performance was shown to be highly related to the polymer microstructure. Tack and peel strength showed a decrease with increasing Lim concentration. Shear strength went through a maximum with a core Lim concentration increase from 0 to 5 phm.

Cellulose nanocrystals (CNCs) are attractive nanomaterials due to their superior mechanical properties, renewability, and natural abundance. Their surface hydroxyl groups, along with surface charges induced during their production, allow CNCs to be easily dispersed in an aqueous medium, especially with sustainable water-based production methods such as emulsion polymerization. Moreover, their surface functionality makes them highly suitable for modification, thereby making them even more versatile. Emulsion polymer latexes are heterogeneous mixtures, having a continuous aqueous phase along with a dispersed organic phase. Latex polymers are used in a wide range of applications such as in coating and adhesive films. Because of the bi-phasic nature of emulsion polymerizations, the surface properties of CNCs play a crucial role in their location relative to the organic phase, and how well-dispersed they are in the cast films. In this thesis, three grades of CNCs (Celluforce Inc.) with either hydrophilic, partially-hydrophobic, or hydrophobic surface properties, were combined with conventional emulsion and miniemulsion polymer formulations to investigate their effect on the properties of pressure sensitive adhesive (PSA) films. In the first instance, hydrophilic CNCs were tested in a seeded semi-batch emulsion polymerization. Using a sequential experimental design, the effects of polar comonomer, surfactant, chain transfer agent, and CNC loading on latex stability and PSA properties were studied. By increasing polymer chain entanglements and the work of adhesion, the hydrophilic CNCs were observed to simultaneously improve the three key properties of acrylic-based PSA films, i.e., tack, peel strength and shear strength. In the second part of this project, we compared the role of hydrophilic and partially-hydrophobic CNCs in PSA property modification. Viscosity measurements and atomic force microscopy revealed differences in the degree of association between the two types of CNCs and the latex particles. Dynamic strain-sweep tests showed that hydrophilic CNC nanocomposites softened at lower strains than their partially-hydrophobic counterparts. This behaviour was confirmed via dynamic frequency tests and modelling of the nanocomposites’ storage moduli, which suggested the formation of CNC aggregates of, on average, 3.8 and 1.3 times the length of CNCs. These results confirmed that the partially-hydrophobic CNCs led to improved CNC dispersion in the PSA films and ultimately, enhanced PSA properties. In the third part of the project, mini-emulsion polymerization (MEP) was used to embed the hydrophobic CNCs within the polymer particles in contrast to the hydrophilic and partially-hydrophobic CNCs which resided mainly in the aqueous phase or near the water-particle interface. Higher CNC loadings led to increased particle size, decreased polymerization rate and number of particles, while only slightly increased the viscosity and the work of adhesion. PSA film properties decreased upon the incorporation of hydrophobic CNCs. Transmission electron microscopy showed that CNCs were expelled from the latex particles at higher loadings, suggesting the incompatibility of the acrylic polymer and the CNCs’ modifying agents. The ability to modify CNCs enables one to achieve a range of hydrophilicity/hydrophobicity. This makes them extremely versatile in a heterogeneous mixture such as in an emulsion polymerization. Because emulsion polymers are used in a wide range of applications with a broad spectrum of properties (i.e., not only as adhesives but as non-tacky coatings), our ability to control CNC location relative to the polymer particles in the latex opens the door to a world of high value-added sustainable polymer products.

A numerical analysis of the loop tack test is presented to study the behavior of the strip and the influence of several factors, and the results are compared with experimental ones. The numerical results can be applied to model the performance of a pressure sensitive adhesive (PSA). Since the simulation of the loop tack test includes geometrical and material nonlinearities, it is solved numerically by the finite element method. The finite element program ABAQUS is used throughout the research. As the teardrop shaped loop is pushed down onto the adhesive and then pulled up, the variation of the loop behavior is investigated using two-dimensional (2D) and three-dimensional (3D) models. A bilinear elastic-plastic constitutive law is used for the strip. The deformation of the pressure sensitive adhesive is approximated as uniaxial extension of independent adhesive strands. A Winkler-type nonlinear elastic foundation and a viscoelastic foundation are used to model the PSA. A nonlinear elastic spring function is used, which is composed of a compression region for the bonding phase and a tension region for the debonding phase. A debonding failure criterion is assumed, in which an adhesive strand will debond when it reaches a certain length. During the bonding phase, it is assumed that the loop is perfectly bonded, and the contact time is not included. Curves of the pulling force versus the top displacement (i.e., tack curves) are obtained throughout the simulation. A parametric study is made with respect to the nonlinear spring function parameters, experimental uncertainties, and strip thickness. Anticlastic bending behavior is shown in the 3D analysis, and the contact patterns are presented. The effects of the elasticity modulus of the PSA for the elastic foundation and the displacement rate for the viscoelastic model are investigated. / Ph. D.

The loop tack test measures the tack (instant grip) of an adhesive. An analytical model of this test seems to be lacking and is the subject of this research. The strip is investigated using several mathematical formulations, and the solutions are obtained numerically. The loop is created from a flexible elastic strip that is bent into a teardrop shape, with its ends clamped together. The strip is tested in a cycle, in which the loop is first pushed onto the surface, compressing the adhesive. Then the loop is pulled up, and gradually debonds from the substrate. The loop is assumed to be nonlinearly elastic and inextensible. The mechanics of the loop tack test are studied in order to determine the impact of various factors on adhesive performance. These factors include the stiffness of the backing, the stiffness and thickness of the adhesive, the elongation of the adhesive before debonding, and the contact time. The relationship between the applied force and the vertical deflection of the loop's ends is determined, as well as that between the applied force and the contact length. Also, the maximum "pull - off" force needed to remove the substrate from the loop is obtained from the results. Shapes of the loop during the cycle are found. This research will increase understanding of the behavior of the adhesive and backing during the loop tack test. With the computer model that has been developed, any set of parameters and conditions can be analyzed, and improvements can be made in the test procedure. / Master of Science

The IKEA customers are looking for new solutions to mount products in their homes and IKEA has embraced the request for this type of applications in bathroom environments as it is of the largest challenges for the customer. Double sided tape has been identified as a possible solution, hence why this project was put together. The research aims to give the reader a deeper understanding regarding double sided tape and the influences of external variables such as material, substrate and surface tension to mention a few. Extensive tests have been carried out where samples from double sided tape suppliers are examined. The test that was developed and carried out in this project aimed to include some of IKEA´s most commonly used materials together with common substrates in bathroom environments. The test data was compiled and the outcome was used to give recommendations to IKEA regarding future product development when using double sided tape and also recommend suitable tape suppliers for continued cooperation.

Orientador: Julio Roberto Bartoli / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-07T21:53:07Z (GMT). No. of bitstreams: 1 Zanin_AileenNicoleFowler_M.pdf: 11356850 bytes, checksum: cf01903240aa482d9b8d8f3559af3823 (MD5) Previous issue date: 2006 / Resumo: Adesivo Sensíveis à Pressão (PSA) são adesivos poliméricos usados principalmente em fitas e etiquetas. De modo geral, existem três tipos de adesivos PSA: a base de solvente, a base d'água e "hot melt". Os adesivos a base de solvente apresentam algumas limitações como flamabilidade e toxicidade, mas ainda são amplamente usados, devido às propriedades finais que apresentam, como boa adesividade a substratos polares c boa adesão com alguns plásticos. Geralmente, os compostos poliméricos para PSA utilizam cargas minerais devido à redução de custo e às propriedades finais que os PSA podem apresentar, como propriedades dielétricas, resistência à umidade e tensão na ruptura. Por outro lado, nanocompósitos estão mostrando grandes vantagens em várias aplicações poliméricas, melhorando suas propriedades térmicas, mecânicas e retardância à chama. Adesivos PSA nanocompósitos a base de solvente foram preparados pelo processo de esfoliação-solução de compostos a base de borracha natural e argilas organicamente modificadas. Um planejamento fatorial de experimentos, 22 com replicata, foi utilizado para verificar a influência dos fatores da composição: concentração e tipos de argilas modificadas, nas propriedades físicas dos adesivos. Um composto adesivo de referencia (PSA convencional) foi também preparado utilizando CaCOH3, carga de uso comum nessas formulações. Os adesivos foram caracterizados através das suas propriedades adesivas (coesão ou "shear", adesão ao aço ou "peel" ,tlato à superfície ou "tack") gel e resistência à propagação de chama. A maioria dessas propriedades apresentou significância estatística em ao menos um dos fatores de composição estudados, tipo ou concentração de nanoargila. Os ensaios de resistência á propagação de chama mostraram melhoria nas propriedades de resistência à propagação da chama em todos os adesivos com argilas modificadas, comparados ao composto de referência. Análises TGA indicaram o mesmo comportamento de variação de massa em função da temperatura para lodos os adesivos. As análises DMTA dos adesivos mostraram diferenças entre os dois tipos de argilas modificadas quanto às suas Tg. Nas análises XRD dos adesivos não foram identificados picos de difração característicos das argilas, talvez devido à diluição das amostras ou até à desejada esfoliação. Nas análises de SEM dos compostos adesivos observou-se uma tênue forma lamelar devido às argilas e as análises EDS dos compostos indicaram a presença de Si e Al, constituintes da argila modificada / Abstract: Pressure sensitive adhesives (PSA) are polymeric adhesives used for mainly in tapes and labels. Usually, there are 3 types of PSA: solvent based, water based and hot melt. Solvent based adhesives have few limitations, like flammability and toxicity, but they are still often used, due to their properties as good adhesion to polar substrates and good bonding with some plastics. The compounds for pressure sensitive adhesives, in general, use fillers due to cost reduction and properties they can give, like dielectric properties, water resistance and tensile strength. On the other side, nanocomposites are showing great advantages on several polymers applications improving thermal resistance, flame retardancy and mechanical properties. Nanocomposites for solvent-based adhesives were prepared by an exfoliation-solution process of natural rubber and organically modified clay compounds. A Design of Experiment (DOE). 22 with replication, was used to verify the influence of compounding factors; concentration and grades of nanoclays.A control adhesive compound was prepared using CaCO3, very common filler for adhesive fonnulations. The PSA were characterized by their adhesive properties (cohesion or shear, adhesion to steel or peel test, tack), gel and flammability. Almost all these properties showed statistical significance at least for one of the compounding factors, grade or concentration of nanociay. The flammability tests showed an improvement on the flame retardancy properties for all the nanoclays adhesives compared to the control compound. TGA analyses showed the same pattern of mass reduction as a function of temperature for all the adhesives. DMTA showed differences between the 2 kinds of nanoclays regarding Tg. XRD analyses did not show any diffraction peak related to the clays, likely due to the diluted samples or even to an exfoliation. SEM analyses showed a slightly lamellar pattern of clays and EDS analyses of the compounds confirmed the presence of Si and Al, elements of the nanoclays / Mestrado / Ciencia e Tecnologia de Materiais / Mestre em Engenharia Química

In this study, novel lamination techniques are introduced for the coating of fabrics in order to enhance their ballistic/needle penetration resistance properties. Pressure sensitive adhesive (PSA) was used to create flexible ballistic composite panels with ultra-high molecular weight polyethylene (UHMWPE) fabric. An increase in processing pressure from 0.1 to 8 MPa significantly improved the ballistic performance against 9 mm FMJ ammunition of UHMWPE composite. The number of layers required to stop the bullet were reduced from 45 to 22 layers after lamination without a significant increase in stiffness. The backface signature (BFS) was reduced from 19.2 mm for the 45 layer neat samples to 11.7 mm for the 25 layer laminated samples pressed at 8 MPa. The second lamination technique used patterned thermoplastic hot film to create flexible UHMWPE composite laminates. Hexagonal patterns were cut through a heat transfer vinyl carrier sheet using a vinyl cutter and was used as a mask between the UHMWPE fabric and hot film during heat treatment in order to have the fabric coated only on those regions. The patterns had a nominal diameter of 27.9 mm with a 1 mm gap between each region. A significant improvement in the ballistic performance of UHMWPE fabric is observed after coating each individual layer with patterned hot film and 25 layers of laminated fabric were sufficient to stop a .357 magnum FMJ ammunition compared to unlaminated neat fabric which required 45 layers to stop the bullet. Patterning of the hot film did not negatively affect the ballistic performance of the composite laminates whilst increasing their flexibility in relation to using plain hot film with no patterning involved. It resulted in a 21% increase in bending angle of the 25 layer samples v and 9.5% reduction in bending length of the single plies which both relate to greater flexibility because a higher bending angle and lower bending length correlates to more flexibility. The same technique of patterning of hot film is used in the lamination of woven cotton fabric to enhance needle penetration resistance properties whilst maintaining the flexibility. Patterns used in this study were either hexagonal or a combination of hexagons and triangles and the nominal diameter ranged from 2.6-13.5 mm. The lamination significantly improved the 25G hypodermic needle penetration resistance of the fabric. By increasing the number of laminated fabric plies from 1 to 2, the needle resistance force increased by up to 150%. However, in comparison to just one layer, the flexibility decreased by about 12% to 26% for two and three layers, respectively. It was observed that reducing the sizes of the patterns improved the flexibility of the samples by up to 30% without compromising the needle penetration resistance. / Thesis / Master of Applied Science (MASc)