Synthesis and analysis of properties of a new core–shell silicon‐containing fluoroacrylate latex

BACKGROUND: Silicon‐containing fluoroacrylate copolymers are potential materials for use in the protection of ancient stone buildings. In the work reported in this paper, a new core–shell silicon‐containing fluoroacrylate latex was prepared through grafting of a fluoroacrylate copolymer latex with polysiloxane. RESULTS: The core–shell silicon‐containing fluoroacrylate latex was successfully synthesized by seed emulsion polymerization and octamethylcyclotetrasiloxane (D₄) ring‐opening polymerization in the presence of a mixed emulsifier consisting of a non‐ionic emulsifier and a novel fluorine‐containing anionic emulsifier sodium perfluoro‐octane sulfonate. Transmission electron microscopy, X‐ray photoelectron spectroscopy, static contact angle measurements and scanning electron microscopy‐energy dispersive X‐ray analysis showed that when the D₄ content was controlled at 2.84–4.36 wt%, the silicon‐containing fluoroacrylate latex presented a uniform sphere core‐shell structure and had strong hydrophobic and oleophobic characters due to the association of both fluorine and silicon atoms on the latex film surface. The film cross‐section exhibited uniform and dense microstructure without any phase segregation. Additionally, thermogravimetric analysis and tensile test results indicated that all the silicon‐containing fluoroacrylate copolymers displayed better thermal stability and higher flexibility. CONCLUSION: The synthetic core–shell silicon‐containing fluoroacrylate latex showed excellent surface properties, thermal stability and flexibility, and has encouraging prospects in application as a protective coating. Copyright © 2009 Society of Chemical Industry     

Preparation and properties of core [poly(styrene‐n‐butyl acrylate)]–shell [poly(styrene–methyl methacrylate–vinyl triethoxide silane)] structured latex particles with self‐crosslinking characteristics

Structured latex particles with a slightly crosslinked poly(styrene‐n‐butyl acrylate) (PSB) core and a poly(styrene–methacrylate–vinyl triethoxide silane) (PSMV) shell were prepared by seed emulsion polymerization, and the latex particle structures were investigated with Fourier transform infrared, thermogravimetric analysis, differential scanning calorimetry, transmission electron microscopy, and dynamic light scattering. The films that were formed from the structured core (PSB)–shell (PSMV) particles under ambient conditions had good water repellency and good tensile strength in comparison with films from structured core (PSB)–shell [poly(styrene–methyl methyacrylate)] latex particles; this was attributed to the self‐crosslinking of CH₂?CH? Si(OCH₂CH₃)₃ in the outer shell structure. The relationship between the particle structure and the film properties was also investigated in this work. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1824–1830, 2006     

Self‐assembly of pH‐responsive acrylate latex particles at emulsion droplets interface

The self‐assembly of pH‐responsive poly (methyl methacrylate‐co‐acrylic acid) latex particles at emulsion droplet interfaces was achieved. Raising pH increases the hydrophilicity of the latex particles in situ and the latex particle acts as an efficient particulate emulsifier self‐assembling at emulsion droplet interface at around pH 10–11 but exhibits no emulsifier activity at higher pH. This effect can be reversibly induced simply by varying the aqueous phase pH and thus the latex emulsifier can be reassembled. The effect factors, including the aqueous phase pH, the surface carboxyl content, ζ‐Potential of the latex particles and oil phase solvent have been investigated. Using monomer as oil phase, the latex particles could stabilize emulsion droplets during polymerization and cage‐like polymer microspheres with hollow core/porous shell structure were obtained after polymerization. The mechanism of the latex particles self‐assembly was discussed. The morphologies of emulsion and microspheres were characterized by optical microscopy, scanning electron microscopy, and transmission electron microscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and properties of core–shell nanosilica/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) latex

A core–shell nanosilica (nano‐SiO₂)/fluorinated acrylic copolymer latex, where nano‐SiO₂ served as the core and a copolymer of butyl acrylate, methyl methacrylate, and 2,2,2‐trifluoroethyl methacrylate (TFEMA) served as the shell, was synthesized in this study by seed emulsion polymerization. The compatibility between the core and shell was enhanced by the introduction of vinyl trimethoxysilane on the surface of nano‐SiO₂. The morphology and particle size of the nano‐SiO₂/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) [P(MMA–BA–TFEMA)] core–shell latex were characterized by transmission electron microscopy. The properties and surface energy of films formed by the nano‐SiO₂/P(MMA–BA–TFEMA) latex were analyzed by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy/energy‐dispersive X‐ray spectroscopy, and static contact angle measurement. The analyzed results indicate that the nano‐SiO₂/P(MMA–BA–TFEMA) latex presented uniform spherical core–shell particles about 45 nm in diameter. Favorable characteristics in the latex film and the lowest surface energy were obtained with 30 wt % TFEMA; this was due to the optimal migration of fluorine to the surface during film formation. The mechanical properties of the films were significantly improved by 1.0–1.5 wt % modified nano‐SiO₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Vi‐PDMS incorporated with protein‐based coatings designed for permeability‐enhanced applications

Functional polydimethylsiloxanes containing vinyl groups (Vi‐PDMS) were used for silicone‐based organic polymers in composites and adhesive formulations. Poly(butyl acrylate/methyl methacrylate/vinyl silicone oil)/casein–caprolactam [P(BA‐MMA‐Vi‐PDMS)/CA‐CPL] nanoparticles were prepared via emulsifier‐free polymerization. The well‐defined core–shell structure of P(BA‐MMA‐Vi‐PDMS)/CA‐CPL nanoparticles was verified by transmission electron microscopy. The results of scanning electron microscopy and contact angle measurements proved that the as‐obtained coatings exhibited porous and hydrophobic properties, which were helpful for superior water vapor permeability. By comparing the appearance of the coatings before and after adhesion analysis, the excellent adhesion strength was proved to be dominated by Vi‐PDMS. The relationship between interface morphology and properties of the resultant coatings was investigated in detail. The nucleation mechanism for this soap‐free emulsion synthesis was also proposed accordingly. These results could help in designing coatings with better surface properties and wider application. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46501.     

Investigation of fluorinated polyacrylate latex with core–shell structure

Fluorinated polyacrylate latices with core–shell structure were prepared by semi‐continuous emulsion polymerization, using a mixed emulsifier system composed of a reactive emulsifier and a small amount of anionic emulsifier. The conversion and chemical components of the final latices were studied by gravimetric methods and Fourier‐transform infrared (FTIR) spectrometry, respectively. The structure of the latex particles was determined by differential scanning calorimetry (DSC), transmission electron microscopy (TEM) and particle size analysis. The latex films exhibited a low surface energy and high water‐contact angles. The surface analysis from X‐ray photoelectron spectroscopy (XPS) revealed that the fluorinated components preferentially self‐organized at the film–air interface. From XPS depth profiling of the film, it was found that a gradient concentration of fluorine existed in the structure of the latex film from the film–air interface to the film–glass interface. Compared with the core–shell structure with a fluorinated core, the core–shell structure with a fluorinated shell was more effective for modifying the properties of the latex films. Copyright © 2005 Society of Chemical Industry     

Interfacially initiated microemulsion copolymerization: One‐stage preparation of poly(n‐butyl methacrylate)–poly(N‐vinyl pyrrolidone) core–shell nanoparticles

Interfacially initiated microemulsion copolymerizations of n‐butyl methacrylate (BMA) and N‐vinyl pyrrolidone (NVP) by the redox initiation couple of benzoyl peroxide and ferrous sulfate were carried out with Tween 80 and n‐butanol as the surfactant and cosurfactant, respectively. Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy were recorded to analyze the chemical composition of the latex particles. Transmission electron microscopy was used to observe the particle morphology and dynamic light scattering to determine the particle size. The results demonstrated that interfacially initiated microemulsion polymerization prompted the copolymerization of the water‐soluble NVP monomer with the oil‐soluble BMA monomer to form core–shell nanoparticles. The influence of the surfactant concentration, BMA amount, and temperature on the particle size and polymerization rate was investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3751–3757, 2006     

PVAc Microspheres via Semicontinuous Emulsion Polymerization: Synthesis,Characterization, Kinetic,and Surface Morphology Studies

Poly (vinyl acetate) (PVAc) latexes are economically important products with many desirable features. They are used as adhesives for porous materials in various processing stages of industries. Synthesis parameters have an important role on the physico-chemical properties of PVAc latexes such as: viscosity, average molecular weight, degree of polymerization, and surface morphology. In this work, PVAc was prepared via semicontinous emulsion polymerization (delayed monomer and initiator addition process) in the presence of ammonium persulfate (APS) as conventional anionic initiator, poly (vinyl alcohol) (PVA) as stabilizer, and sodium lauryl sulfate (SLS) as anionic emulsifier. The surface morphology of PVAc microspheres was, examined using a scanning electron microscope (SEM) and atomic force microscope (AFM). It is evident from the SEM photographs that all the particles became microspheres and are uniform in shape. The use of AFM for imaging of polyvinyl acetate confirms a typical sphere polymer. The effect of changes in the different parameters such as concentration of emulsifier, initiator concentration, and presence or absence of buffer on the vinyl acetate (VAc) conversion, the steady state polymerization rate, the viscosity-average molecular weight, and the final latex viscosity of synthesized PVAc were investigated. The effects of anionic emulsifier on the synthesized PVAc are also compared with those obtained by the nonionic emulsifier. The comparison indicated that the VAc monomer conversion and the final latex viscosity of the anionic system were higher than for the nonionic system but the viscosity-average polymer molecular weight of the anionic system was lower than that of the nonionic system. The adhesive strength of the synthesized PVAc latex was examined and the load and deflection data were reported.     

Preparation and characterization of trilayer core–shell polysilsesquioxane–fluoroacrylate copolymer composite emulsion particles

Polysilsesquioxane–fluoroacrylate copolymer [poly(methyl methacrylate)–butyl acrylate–dodecafluoroheptyl methacrylate)] (FPSQ) composite latex particles with a trilayer core–shell morphology were manufactured by seeded emulsion polymerization, where PSQ latex particles bearing reactive methacryloxypropyl moieties were first produced by the hydrolysis‐condensation of (3‐methacryloxypropyl)trimethoxysilane, and then they were utilized as seeds, with methyl methacrylate, butyl acrylate, and dodecafluoroheptyl methacrylate as the inner and outer shell monomers. Fourier‐transform infrared spectra and ¹H‐NMR confirm the structure of the FPSQs. Transmission electron microscopy and scanning electron microscopy demonstrate that the obtained composite emulsion particles emerge with the trilayer core–shell pattern. Due to the anchoring of PSQ nanoparticles, the thermal stabilities of the FPSQ films are strengthened, and the resistance to heat is gradually improved along with the increase of the fluoroacrylate dose in the polymer matrix composite. X‐ray photoelectron spectroscopy, atomic force microscopy (AFM), and hydrophobicity investigations indicate that the fluorinated chain segments tend to concentrate at the film–air two‐phase interface. In addition, the AFM result denotes that importing more fluorine into the FPSQ hybrid material will engender greater phase separation and enrichment of the fluoroalkyl segments and a rougher morphology. Thus, the water contact angle of the FPSQ film can ultimately reach 121.4°. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44845.     

Chemical components and properties of core–shell acrylate latex containing fluorine in the shell and their films

Core–shell acrylate latices containing fluorine in the shell were prepared by semicontinuous emulsion polymerization. The chemical components of the latices were determined by Fourier transform infrared, ion‐selective electrode analysis, and differential scanning calorimetry. The average size and morphology of the latex particles were characterized by photocorrelation spectroscopy and transmission electron microscopy, respectively. The latex particles were mainly composed of a non‐fluorine core and a fluorinated shell. The dynamic water contact angles of the latex films from the Wilhelmy method indicated that the latex films containing fluorine in the shell could be wetted by water only with difficulty. The amount of the fluoromonomer played an important role in the modification on the water contact angles, water absorption, and thermal stability of the latex films. In comparison with a random structure, the core–shell structure was more effective for improving the thermal properties of the latex films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 107–114, 2006     

Synthesis and properties of fluorine–silicon modified polyacrylate hybrid latex particles with core–shell structure obtained via emulsifier‐free emulsion polymerization

A core–shell fluorine–silicon modified polyacrylate hybrid latex was successfully prepared via emulsifier‐free emulsion polymerization. The chemical composition and core–shell morphology of the resultant hybrid particles were investigated using ¹H NMR and Fourier transform infrared spectroscopies and transmission electron microscopy (TEM), respectively. TEM analysis indicated that the core–shell hybrid particles were uniform with narrow size distributions. The particle size and zeta potential decreased with an increase of alkylvinylsulfonate surfactant from 2.5 to 6.0 wt%. X‐ray photoelectron spectroscopy revealed that fluorine concentrated preferentially at the film surface during a film‐formation process. The film formed from the fluorine–silicon modified polyacrylate showed much higher thermal stability than a film formed from polyacrylate and fluorine‐modified polyacrylate. Contact angle results showed that a finished fabric had remarkable water repellency. © 2015 Society of Chemical Industry     

Preparation of organic–inorganic nanocomposites with core‐shell structure by inorganic powders

Organic–inorganic nanocomposites with core‐shell structure were prepared in two steps. In the first step, the latex particles in the semibatch emulsion polymerization of butyl methacrylate (BMA), in the presence of methacrylic acid (MAA), were prepared. Small amounts of acrylic acid incorporated into the latex to have better interaction between the surface of particles and inorganic phase. MAA also increased the latex stability and decreased the amount of coagulum. In the second step, the core‐shell structures were prepared by coating the latex particles with three types of inorganic powders. Pectin coated precipitated calcium carbonate, alumina, and silica. The examinations show that pectin‐coated calcium carbonate has the best response than other types of calcium carbonate. Alumina was the second type of inorganic powder that was used for coating the core particles. Silicagel and fumed silica (Aerosil) were used for coating by silica. Scanning electron microscopy and transmission electron microscopy showed the particle morphology and the core‐shell structure, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Effect of ethyleneglycol dimethacrylate crosslinker on the performance of core‐double shell structure poly(vinyl acetate‐butyl acrylate) emulsion

Core‐double shell structure poly(vinyl acetate‐butyl acrylate) emulsion was prepared by semicontinuous emulsion polymerization, and the effects of ethyleneglycol dimethacrylate crosslinker (EGDMA) on the emulsion particle structure and film performance were studied systematically. The emulsion particles' structure was characterized by transmission electron microscopy and Fourier transform infrared spectroscopy, and the particle size and distribution were characterized by Zeta potential—particle analyzer, as well as analysis of the film mechanical properties, water resistance, thermal properties, and so on. The results show that, when 0.1 and 0.5% EGDMA were added to the inner‐shell and outer‐shell reaction stage under the core‐double shell P(VAc‐BA) emulsion preparation process, respectively, it led to a more clear core‐double shell structure and a larger particle size (about 500–800 nm) of emulsion particles, and the comprehensive performance of the P(VAc‐BA) emulsion showed better. This work provided some insight into modifying the surface properties of the emulsion particles, which may expand the application field of the emulsion. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41899.     

Preparation of core–shell latex for the pigmented ink of textile inkjet printing

A core–shell latex comprising poly(butyl acrylate) as core and poly(styrene‐methyl methacrylate) as shell was synthesized by emulsion polymerization using allyloxy nonylphenoxy propanol polyoxyethylene ether ammonium sulfonate (ANPS) as emulsifier. Transmission electron microscope, differential scanning calorimeter, and thermogravimetric analyses suggested the prepared latex had a core–shell structure. The particle size of the core–shell latex was about 102.8 nm with a molar ratio of butylacrylate, methyl methacrylate, and styrene at 6 : 2 : 2, a mass ratio of ANPS and monomers, ammonium persulfate and monomers at 15% and 1.0%, respectively. The core–shell latex showed high centrifugal stability and excellent freeze‐thaw stability. The clogging nozzle rate of the pigmented ink containing 20 wt % core–shell latex was small, whereas the printed fabrics with this pigmented ink exhibited high rub and washing fastness. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Particle morphology and NMR structure of polymethylmethacrylate/polystyrene emulsifier‐free core–shell cationic latices in the presence of DBMEA

In the absence of emulsifier, we prepared stable emulsifier‐free polymethylmethacrylate/polystyrene (PMMA/PSt) copolymer latex by batch method with comonomer N,N‐dimethyl, N‐butyl, N‐methacryloloxylethyl ammonium bromide (DBMEA) by using A1BN as initiator. The size distribution of the latex particles was very narrow and the copolymer particles were spherical and very uniform. Under the same recipe and polymerization conditions, PMMA/PSt and PSt/PMMA composite polymer particle latices were prepared by a semicontinuous emulsifier‐free seeded emulsion polymerization method. The sizes and size distributions of composite latex particles were determined both by quasi‐elastic light scattering and transmission electron microscopy (TEM). The effects of feeding manner and staining agents on the morphologies of the composite particles were studied. The results were as follows: the latex particles were dyed with pH 2.0 phosphotungestic acid solution and with uranyl acetate solution, respectively, revealing that the morphologies of the composite latex particles were obviously core–shell structures. The core–shell polymer structure of PMMA/PSt was also studied by ¹H, ¹³C, 2D NMR, and distortionless enhancement by polarization transfer, or DEPT, spectroscopy. Results showed that PMMA/PSt polymers are composed of PSt homopolymer, PMMA homopolymer, and PMMA‐g‐PSt graft copolymers; results by NMR are consistent with TEM results. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1681–1687, 2005     

Preparation and characterization of core‐shell nanoparticles containing poly(chlorotrifluoroethylene‐co‐ethylvinylether) as core

Core shell latex particles with a glassy core and a low T_g polymeric shell are usually preferred. More so, the glassy core happens to be a fluoropolymer with a shell polymer that helps in processability. We describe here the preparation and characterization of core shell nanoparticles consisting of poly(chlorotrifluoroethylene‐co‐ethylvinylether) as core encapsulated in poly(styrene‐acrylate) copolymer shell using seeded emulsion polymerization method under kinetically controlled monomer starved conditions. Properties of the emulsion using surfactants (fluoro/conventional) and surfactant free conditions were investigated. Average size (100 nm), spherical shape and core–shell morphology of the latex particles was confirmed by dynamic light scattering and transmission electron microscopy. Absence of C? F and C? Cl peaks in X‐ray photoelectron spectroscopy proves that cores are completely covered. Polymerization in the presence of fluorocarbon surfactant was found to give optimum features like narrow size distribution, good shell deposition and no traces of agglomeration. Films of core shell latex particles exhibited improved transparency and enhanced water contact angles thus making them suitable for applications in various fields including coatings. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of poly(methyl methacrylate–butyl acrylate–acrylic acid)/polyaniline core–shell nanoparticles in miniemulsion media

Conductive polymer particles, polyaniline (PANI)‐coated poly(methyl methacrylate–butyl acrylate–acrylic acid) [P(MMA–BA–AA)] nanoparticles, were prepared. The P(MMA–BA–AA)/PANI core–shell complex particles were synthesized with a two‐step miniemulsion polymerization method with P(MMA–BA–AA) as the core and PANI as the shell. The first step was to prepare the P(MMA–BA–AA) latex particles as the core via miniemulsion polymerization and then to prepare the P(MMA–BA–AA)/PANI core–shell particles. The aniline monomer was added to the mixture of water and core nanoparticles. The aniline monomer could be attracted near the outer surface of the core particles. The polymerization of aniline was started under the action of ammonium persulfate (APS). The final product was the desired core–shell nanoparticles. The morphology of the P(MMA–BA–AA) and P(MMA–BA–AA)/PANI particles was characterized with transmission electron microscopy. The core–shell structure of the P(MMA–BA–AA)/PANI composites was further determined by Fourier transform spectroscopy and ultraviolet–visible measurements. The conductive flakes made from the core–shell latexes were prepared, and the electrical conductivities of the flakes were studied. The highest conductivity of the P(MMA–BA–AA)/PANI pellets was 2.05 S/cm. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Polystyrene‐montmorillonite core–shell particles via Pickering emulsion polymerization and their use as reinforcing additives for polypropylene and ethylene vinyl acetate

Solid particles can be used as stabilizers for oil/water (o/w) emulsions instead of the conventional surfactants. Emulsion polymerization of styrene, as an example of polymerizable oil, was started in the current study after ultrasonication of the monomer into aqueous phase with aid of montmorillonite nanoplatelets as solid stabilizer. Imaging using a field emission scanning electron microscopy equipped with energy dispersive X‐ray unit as well as transmission electron microscopy proved the formation of polystyrene/montmorillonite as core–shell hybrid latex particles via Pickering mode of emulsification. The mechanical properties of polypropylene (PP) and ethylene vinyl acetate copolymer (EVA) were studied after addition of various loadings of these hybrids (2, 4, 8, 12, and 14 wt%). It could be ensured that the tolerance of PP towards phase separation caused by the insertion of the core–shell particles was higher than that of EVA, which translates into different extents of reinforcements. POLYM. ENG. SCI., 55:1546–1552, 2015. © 2015 Society of Plastics Engineers     

Rubber modification of unsaturated polyester resin with core–shell rubber particles: Effect of shell composition

Poly(butyl acrylate)/poly(vinyl acetate‐co‐methyl methacrylate) PBA/P(VAc‐co‐MMA) core–shell rubber particles with various shell compositions, i.e., VAc/MMA weight ratios, were used to toughen unsaturated polyester. The morphology and surface‐free energy of the rubber particles were determined by transmission electron microscopy (TEM) and contact angle measurements, respectively. The effect of shell structure on the dispersion state of rubber particles inside the unsaturated polyester resin was studied by scanning electron microscopy and TEM. Increasing MMA units in the shell changed the particle dispersion state from small agglomerates or globally well‐dispersed particles to large aggregates in the cured‐resin matrix. For the blends that contain 5 wt% rubber, the highest un‐notched impact toughness, stress‐intensity factor (K_IC), and fracture energy (G_IC) were observed for the blend containing PVAc shell particles. The results showed that by increasing the particle level from 5 to 10 wt%, the highest K_IC and G_IC values were obtained for the blend containing rubber particles with VAc/MMA (80/20 wt/wt) copolymer shell. The crack‐tip damage zone in the neat and rubber‐modified unsaturated polyester resins was observed by means of transmission optical microscopy. In addition, using PVAc shell particles exhibited a minimum reduction in the volume shrinkage and tensile properties of the rubber‐modified resin. POLYM. ENG. SCI., 52:1928–1937, 2012. © 2012 Society of Plastics Engineers     

Emulsion polymerization of styrene and DEAEMA with a core–shell structure

Polystyrene–poly(N,N‐diethylamino ethyl methacrylate) (PS–PDEAEMA) particles with a core–shell morphology were prepared by seeded emulsion polymerization. Poly(oxyethylene) (POE) (n = 15 and 30) nonyl phenol and sodium lauryl sulfate (SLS) were used as emulsifiers. These two emulsifiers were selected in order to study the effect of nonionic and ionic emulsifiers on the reaction because of the basic character of DEAEMA. The core–shell morphology was investigated independently in the presence of water‐soluble potassium persulfate (KPS) and of oil‐soluble azobisisobutyronitrile (AIBN). The morphologic structure of the particles was studied using scanning electron microscopy and transmission electron microscopy. The latex particles and the polymers were characterized by differential scanning analysis, thermogravimetric analysis, and gel permeation chromatography. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1977–1985, 2000