Latex film formation: atomic force microscopy and theoretical results

We have critically examined the kinetics of latex film formation using an atomic force microscope to obtain corrugation height data as a function of time, temperature, molecular weight, particle size, etc. The results show that the film forming process obeys viscoelastic time/ temperature superposition principles, thus indicating a direct relationship between the kinetics of film formation and rheological properties. Film formation kinetics are examined under ‘wet’ and ‘dry’ conditions, with film formation occurring almost ten-times faster under wet conditions than dry. This proves for the latex system examined that capillary pressure from the water meniscus is the dominant driving stress for film formation. Past theories for latex film formation are reviewed, and problems and deficiencies are noted. A new theory for film formation from a dry latex system is presented, which is based on the use of the Boltzmann Superposition Principle to relate the changing stress and strain fields as the latex particles deform. The predictions of theory and the experimental data show excellent agreement over nearly four decades of time.     

Stress development and film formation in multiphase composite latexes

Designed appropriately, multiphase soft-core/hard-shell latex particles can achieve film formation without the addition of a coalescing aid, while preserving sufficient film hardness. Achieving optimal performance in these materials requires an understanding of how particle morphology affects film formation and stress development in the film. In this study, soft-core/hard-shell latex particles with different shell ratios, core and shell glass transition temperatures (T _gs), and particle sizes (63–177 nm) were synthesized using a two-stage emulsion polymerization. The film formation behavior of the composite particles was investigated with cryogenic scanning electron microscopy, atomic force microscopy, and measurements of the minimum film formation temperature (MFFT). Results show that film formation was enhanced for particles with thinner hard shells, smaller particle size, and a smaller difference in T _g between the core and shell polymers. For example, the MFFT decreased and the particle deformation increased for particles with thinner shells and smaller particle sizes. Stress development during drying was characterized using a cantilever beam bending technique. A walled cantilever design was used to monitor stress development without the complication of a lateral drying front. The film formation behavior and stress development correlated well with practical paint properties like scrub resistance and gloss.     

Interfacial aspects of strength development in poly(methyl methacrylate)-based latex systems

Film formation from poly(methyl methacrylate) (PMMA) latex and PMMA copolymer latex incorporating N-(iso-butoxymethyl)acrylamide (IBMA) or methacrylic acid (MAA) has been investigated in terms of the development of tensile strength as a function of annealing time and temperature. Tensile strength is developed through a combination of macromolecular interdiffusion and interfacial crosslinking. The relative rates of interdiffusion vs. crosslinking reactions were studied as a function of temperature and the chemical nature and concentration of the IBMA and MAA functional groups. For low concentrations of these two functional monomers it appears that polymer chain interdiffusion between adjacent latex particles during the film formation process dominates the kinetics of strength development. However, at higher IMBA and MAA concentrations, the higher glass transition temperature at the latex particle surface and intraparticle crosslinking hinders interdiffusion, as reflected by differences in the power law exponent values obtained from the log-log dependence of tensile strength on annealing time. The power law exponents were higher in the case of PMMA than for both IBMA- and MAA-containing copolymers. There was a greater influence temperature on the tensile behavior for the MAA copolymer system as compared to the IBMA copolymer. In the interfacially crosslinked latex polymer system, there is competition between the interdiffusion and crosslinking mechanisms in determining the final mechanical strength of films during the annealing process. © 1995 John Wiley & Sons, Inc.     

Influence of co-solvent content on electro-deposition behavior of acrylic lattices of different glass transition temperatures

The influence of co-solvent content on the constant-voltage electro-deposition behavior of three acrylic lattices was investigated. It was found that co-solvent effect is system-specific and the type and the extent of the influence depend on the specific features of the latex itself, specially its glass transition temperature, T_g. For a low-T_g high molecular weight latex, the addition of co-solvent makes the electro-coagulates more sticky but it does not show a quick influence on the deposition behavior. In contrast for higher T_g lattices the influence is more pronounced. For medium and high-T_g lattices, the co-solvent was found to have a significant influence on the electro-deposition behavior and the film morphology.     

On the role of colloidal crystal-like domains in the film forming process of a carboxylated styrene-butadiene latex copolymer

Environmental scanning electron microscopy (ESEM) was employed to study the mechanism of film formation of a carboxylated styrene-butadiene latex copolymer with a glass transition temperature (T_g) of 6 °C. ESEM allows the investigation of wet samples in their native state which is required to study the drying process of latex dispersions. The film forming process was tracked by time-dependent ESEM monitoring of the latex particle morphology and by observing the different stages occurring during the drying process. The focus of our study was an analysis of the three-dimensional (3D) arrangement of the latex particles and a comparison of their appearance on the surface and in the center of the coalesced film. It was found that in the course of film formation, the latex particles arrange in domains which are similar to colloidal crystals. Such domains occur at the stage of dense particle packing. Particle coalescence appears to begin first in these domains before a continuous and homogeneous film is formed which then spreads across the entire substrate. The results suggest that for our carboxylated styrene-butadiene copolymer the current model known for the film forming mechanism which includes four main steps should be complemented by two additional ones, namely the arrangement of particles in crystal-like domains and the beginning of coalescence within these domains. This specific behavior only occurs for monodisperse latices.     

Role of particle size on latex deformation during film formation

The ability of latex particles to deform and coalesce to form an integral film upon drying is an important property in many latex coating applications. Many theories have been proposed to account for the origin of the deformation forces. The capillary forces which depend inversely on particle size have been accepted as important for latex deformation and film formation. The minimum film forming temperature (MFFT) has been found to be a function of the particle size of latexes and has been used as evidence that the capillary forces are responsible for film formation. In this study, the deforming force at MFFT has been determined from the moduli of water-equilibrated latex polymers. No particle size dependence was observed. The magnitude of the deforming forces was at least an order of magnitude lower than that predicted by the capillary force theory. Electron microscopy of film formed below the MFFT, a condition that corresponds to early stage film formation, showed significant deformation, indicating that at the beginning of film formation, forces of magnitude predicted by the capillary force theory are present. However, the magnitude of the forces decreases rapidly as film formation progresses. The MFFT particle size dependency can be explained by the difference in the degree of water plasticization. Evidence that latexes of different particle size were plasticized by water to different extents was determined from the T_gs of the latex emulsions. Presented at the 76th Annual Meeting of the Federation of Societies for Coalings Technology, on October 15, 1998, in New Orleans, LA. Emusion Polymers Research 1604 Building, Midland, MI 48674.     

Synthesis and properties of branched organosilicon-acrylate copolymer latexes

Summary Stable organosilicon-acrylate copolymer latexes with high silicon content were prepared by seeded semibatch emulsion polymerization of butyl acrylate (BA), methyl methacrylate (MMA) with a novel branched organosilicon monomer 3-methacryloxypropyl tris(trimethylsiloxy) silane (MPTS). Monomer conversion, evolution of the particle size and its distribution were monitored by dynamic light scattering. The effects of MPTS on the polymerization kinetics, the nucleation mechanism and properties of latex were investigated. The results indicated that, in addition to micellar nucleation, a coagulative nucleation step was also observed as a result of the addition of the organosilicon monomer, accordingly, the particle number of the silicon-acrylate latexes increased, the average particle diameter decreased and the polymerization rate accordingly increased compared to those of the acrylate latexes without organosilicon monomer. Moreover, the particle size distribution presented bimodal curves, which indicated that there were large particles formed at an early stage. However, the particle size distribution curves became monomodal at the later stage, and the final latex shows a narrow particle size distribution. It was found that the properties of latex and latex film were obviously influenced by MPTS content. With increasing MPTS content, latex film glass transition temperature and water absorption ratio decreased, the degradation temperature and water contact angle were increased. Hence, the resulting latex films containing MPTS showed lower glass transition temperature and excellent water-resistance, which probably due to the incorporation of the bulky branched hydrophobic group of MPTS into the copolymer chains.     

Surfactant concentration and morphology at the surfaces of acrylic latex films

The final outcome of surfactants during latex film formation is a topic of ongoing concern and interest. In this study of an acrylic latex containing an anionic surfactant, two notable phenomena are observed. (1) A higher surfactant concentration is present at the air surface of the latex films, regardless of the film-forming temperature and time. In some cases, surfactant is not visible in an atomic force microscope (AFM) image as a separate phase, but compositional profiles obtained with Rutherford backscattering spectrometry (RBS) reveal an enhanced concentration of surfactant over a depth from the surface that is comparable to the latex particle diameter. (2) The surfactant features that are imaged with the AFM evolve from a thin uniform layer, to a ‘finger-like' morphology, to small flat droplets, and finally to larger, hemispherical ‘blobs.' We suggest that surfactant is first deposited from the air/water interface onto the latex surface during the drying process. During this progression in the morphology of the surfactant, the ratio of the surface area-to-volume decreases. We speculate that this phenomenon is driven by a reduction in surface energy.     

Acetoacetoxy functionalized natural rubber latex capable of forming cross-linkable film under ambient conditions

This work demonstrates that natural rubber (NR) latex particles containing acetoacetoxy (AcAc) groups are able to undergo cross-linking upon film formation at ambient temperature by reaction with glutaraldehyde (GTA). Natural rubber latex grafted with poly(acetoacetoxyethyl methacrylate) (NR-g-PAAEM) was synthesized by seeded emulsion polymerization, using benzoyl peroxide (BPO) as an initiator in free radical polymerization. The degree of grafting of PAAEM in the graft copolymers was evaluated by ¹H NMR technique. Transmission electron microscope (TEM) was used for investigation the particle morphology of the grafted NR latex. Since the AcAc groups are intentionally attached to the NR particles providing sites of cross-linking at ambient temperature, the cross-linking ability of these sites by reaction with GTA was then investigated. The results revealed that the latex film of NR-g-PAAEM with the addition of GTA had a much higher tensile strength in comparison with the film without GTA. The surface morphology of the NR-g-PAAEM latex film formed in the absence and presence of the GTA cross-linker was also investigated using atomic force microscopy (AFM). By GTA addition into the NR-g-PAAEM latex before film formation, an increase in the root-mean-square (RMS) roughness of the surface of the latex film was observed. Moreover, it was also observed that the NR-g-PAAEM films with the addition of GTA had higher activation energy for thermal degradation than that without the cross-linker. This confirms that the cross-linking reaction took place in the NR-g-PAAEM latex film as a result of its reaction with the GTA.     

Film formation from pigmented latex systems: Mechanical and surface properties of ground calcium carbonate/functionalized poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) latex blend films

The mechanical and surface properties of films prepared from model latex/pigment blends were studied using tensile tests, surface gloss measurements, and atomic force microscopy. Functionalized poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) [P(BMA/BA)] and ground calcium carbonate (GCC) were used as latex and extender pigment particles, respectively. The critical pigment volume concentration of this pigment/latex blend system was found to be between 50 and 60 vol % as determined by surface gloss measurement and tensile testing of the blend films. As the pigment volume concentration increased in the blends, the Young's modulus of the films increased. Nielsen's equations were found to fit the experimental data very well. When the surface coverage of carboxyl groups on the latex particles was increased, the yield strength and Young's modulus of the films both increased, indicating better adhesion at the interfaces between the GCC and latex particles. When the carboxyl groups were neutralized during the film formation process, regions with reduced chain mobility were formed. These regions acted as a filler to improve the modulus of the copolymer matrix and the modulus of the resulting films. The carboxyl groups on the latex particle surfaces increased the surface smoothness of the films as determined by surface gloss measurement. When the initial stabilizer coverage of the latex particles was increased, the mechanical strength of the resulting films increased. At the same time, rougher film surfaces also were observed because of the migration of the stabilizer to the surface during film formation. With smaller‐sized latex particles, the pigment/latex blends had higher yield strength and Young's modulus. Higher film formation temperatures strengthen the resulting films and also influence their surface morphology. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4550–4560, 2006     

Study on the synthesis of poly(methyl methacrylate)–poly(methacrylic acid) composite latex and their humidity sensitive properties

The composite latex particles of poly(methyl methacrylate)–poly(methacrylic acid) [poly(MMA–MAA)] were synthesized through either soapless seeded emulsion polymerization or a soapless emulsion copolymerization technique. The reaction kinetics, morphology, and size of latex particles, composition, glass transition temperature (T_g), and molecular weight of polymer products were studied under different experimental conditions. Moreover, this work also focused on the humidity‐sensitive properties of the polymer films fabricated by melting under the temperature of 200°C and followed by chemical modification with aqueous solution of NaOH. It is confirmed that there exists both an optimum ratio of hydrophilic to hydrophobic monomers and the initial structure of the latex particle to provide the humidity‐sensitive polyelectrolyte film with excellent water resistivity and good sensitivity to humidity. Besides, little hysteresis and quick response were observed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 47–57, 1999     

Structure and properties of multiphase particles and their impact on the performance of architectural coatings

Aqueous dispersions used as binders in low-pigmented solvent-free paint formulations have to cope with the challenge to simultaneously guarantee an excellent film formation and appearance as well as good block resistance and hardness. One strategy to fulfill these contradictory requirements is the employment of multiphase particles.

In this work it is proved that the structure of latex particles, synthesized by a two-stage emulsion polymerization process, can be correlated to the morphology and properties of the dispersion films as well as to the application properties of the corresponding paint films.

Two sets of model dispersions were made. In the first set, the hard/soft ratio was varied, in the second set the amount of the AA. The structure of the particles was determined by TEM, and a morphology map was derived. AFM demonstrated a clear correlation between the particle structure and the morphology of the latex film. Dynamic mechanical analyses verified the presence of two distinct polymers with the hard phase acting as a transparent filler. For the hard/soft series, the properties of the dispersion films such as block resistance, gloss and hardness could be attributed to their structure. A closer look on the block behavior revealed that it can be related to the tack and surface roughness of the dispersion film, but not to its internal strength. Solvent free emulsion gloss paints were formulated, and application tests performed. The properties of the paint films correlated very well with those of the dispersion films. The test results clearly show that dispersions of multiphase particles enable the formulation of solvent free paints with excellent film-forming ability in combination with high block resistance, hardness and gloss.     

Film formation from pigmented latex systems: Drying kinetics and bulk morphologies of ground calcium carbonate/functionalized poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) blend films

The drying kinetics and bulk morphology of pigmented latex films obtained from poly(n‐butyl methacrylate‐co‐n‐butyl acrylate) latex particles functionalized with carboxyl groups and ground calcium carbonate blends were studied. Latex/pigment blends with higher carboxyl group coverage on the latex particle surfaces dried faster than films with few or no carboxyl groups present. The latex/pigment dispersions also dried faster when there was more stabilizer present in the blend system because of the hydrophilic nature of the stabilizer. The net effect of increasing the pigment volume concentration in the blend system was to shorten the drying time. The bulk morphologies of the freeze‐fractured surfaces of the pigmented latex films were studied with scanning electron microscopy. Scanning electron microscopy analysis showed that increased surface coverage of carboxyl groups on the latex particles in the latex/pigment blends resulted in the formation of smaller pigment aggregates with a more uniform size distribution in the blend films. In addition, the use of smaller latex particles in the blends reduced the ground calcium carbonate pigment aggregate size in the resulting films. Scanning electron microscopy analysis also showed that when the initial stabilizer coverage on the latex particles was equal to 18%, smaller aggregates of ground calcium carbonate were distributed within the copolymer matrix of the blend films in comparison with the cases for which the initial stabilizer coverage on the latex particles was 8 or 36%. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2267–2277, 2006     

Studies on polymer latex films: I. A study of latex film morphology

Polymer films have been formed from poly (butyl methacrylate) latices prepared by surfactant-free emulsion polymerisation. The latices having also been cleaned by microfiltration constitute model colloid particles and hence form ‘model’ films. A novel freeze fracture replication and transmission electron microscopy technique was employed to study film morphology. It demonstrated the presence of interparticle boundaries between latex particles deformed into dodecahedra and the particle packing order without the need for a staining technique. The time and temperature of film formation and storage was shown to affect the degree of particle coalescence. Solvent cast films were also studied for comparison purposes.     

水性环氧丙烯酸酯乳液涂层成膜性能

采用细乳液聚合法制备了环氧丙烯酸酯复合乳液,考察了固化温度、固化时间及磷酸酯乳化剂含量对环氧丙烯酸酯复合涂膜性能的影响,结果表明环氧丙烯酸酯复合乳胶粒子呈均匀的球形结构,且平均粒径分布在150 nm左右。当固化温度为120℃、固化时间为2 h、磷酸酯乳化剂含量为3%时,涂层的耐腐蚀性较好。研究了复合乳液的成膜过程和防腐蚀机理,通过复合乳液与金属底材形成致密的钝化膜,阻隔水分子和无机离子的浸入,提高了涂层的防腐性能。     

An ESEM investigation of latex film formation in cement pore solution

Environmental scanning electron microscopy (ESEM) and complementary methods were employed to study the time dependent film formation of a latex dispersion in water and cement pore solution. First, a model carboxylated styrene/n-butyl acrylate latex dispersion possessing a minimum film forming temperature (MFFT) of 18 °C was synthesized in aqueous media via emulsion polymerization. Its film forming property was at a temperature of 40 °C, studied under an ESEM. The analysis revealed that upon removal of water, film formation occurs as a result of particle packing, particle deformation and finally particle coalescence. Film formation is significantly retarded when the latex dispersion is present in cement pore solution. This effect can be ascribed to adsorption of Ca²⁺ ions onto the surface of the anionic latex particles and to interfacial secondary phases. This layer of adsorbed Ca²⁺ ions hinders interdiffusion of the macromolecules and subsequent film formation of the latex polymer.     

Latex characterization by atomic force microscopy

Ways, benefits and limitations of extracting the form and size of single latex particles or particle size distributions out of the surface topography of non-coalesced latex films obtained by atomic force microscopy (AFM) are discussed. The general ways to generate the desired information out of topographical information in terms of height, surface curvature and lateral extensions are shown for idealized particles and measurement conditions. The different sources of information are evaluated for practical use and the analysis of particle size distributions is demonstrated by practical examples. The information content in lateral particle dimensions is shown to be the most advantageous for practical use. Determination of latex particle size distributions by AFM is shown to be an interesting alternative to the arsenal of available methods with respect to exactness of results, time consummation and instrumentation costs.     

Natural rubber latex modification by sodium polyphosphate: a SPM study on the improved latex adhesion to glass sheet

Addition of sodium polyphosphate (NaPP) to natural rubber latex at 0.4 weight ratio improves the adhesion of cast latex dry films to flat glass surfaces. Rubber-polyphosphate dispersions were analyzed by turbidimetric titration, PCS and ultramicroscopy, and the results indicate the formation of two domains within the latex-polyphosphate dispersions: one domain has higher rubber particle content than the other. Thick rubber films were examined by AFM, scanning electric potential and modulated force microscopy. The images show that rubber film morphology is completely altered by NaPP addition. Two types of domains are observed in the dry latex film: one type carries excess positive charges and is harder than the other, negative domains. Both domains are compatible, as shown by the extensive interfaces observed in all images observed. In the latex-glass joints, the positive domains concentrate in the vicinity of the negative glass surface, thus making an electrostatic contribution to glass-latex adhesion.     

微波辐射强化制备含氟硅丙烯酸酯共聚物乳液

采用多步种子乳液聚合法,以丙烯酸丁酯、甲基丙烯酸甲酯、g-(甲基丙烯酰氧)丙基三甲氧基硅烷和甲基丙烯酸六氟丁酯为原料在微波辐射下制备了核-壳型含氟硅丙烯酸酯共聚物乳液. 并研究了共聚物的结构、乳胶粒的形态和聚合过程中粒径的变化. 结果表明,所得乳胶粒子呈核-壳结构,与常规加热相比,微波的引用能加快反应速率,形成核-壳结构. 壳层富集含氟硅聚合物的核-壳形态有利于含氟硅结构单元在聚合物膜表面的分布,当氟硅单体为6%(w)时,乳胶膜对水的接触角达91.3o. 加入氟硅组分显著提高了聚合物膜的耐水性,当其含量从0增大到18%时,乳胶膜的吸水率从20.1%降低到3.54%.     

Experimental investigation on mechanisms of fine particles generation for the Borealis Borstar multistage olefin polymerization process

Simultaneous production of large amount of undesired fine particles is a big trouble in the Borstar multistage olefin polymerization process. Aiming at reducing the fine particles, the formation mechanism and formation location of the fine particles were thus studied. First, the influence of catalyst nature was considered. Second, the ash content, bulk density, morphology, and molecular weight distribution of polyethylene with different particle sizes from the small‐scale loop prepolymerization reactor, supercritical loop reactor, and gas phase fluidized bed reactor were studied, respectively. In combination with particle growth model, scanning electron microscope, gel permeation chromatography, and laser particle size analyzer, the particle morphology and growth kinetics were investigated. The results showed that fine particles were mostly generated in the supercritical loop reactor, and were significantly affected by the particle size distribution, residence time distribution, and particle fragmentation of the catalyst. Furthermore, scanning electron microscope images showed the catalysts with low activity tended to generate more fine particles. Based on these results, several strategies for reducing the amount of fine particles were proposed, which could be applied in the industrial process. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46589.