Copper Phthalocyanine Pigment Research Articles

Accumulation and Potential Remediation of Copper in Golf Course Putting Greens

The objective of this study was to determine the potential accumulation of copper (Cu) within a USGA golf green profile and analyze potential remediation techniques of soils containing toxic Cu concentrations. Accumulation study utilized: copper phthalocyanine pigment (Par), copper hydroxide (Junction DF), varying concentrations of copper sulfate (CuSO4) within irrigation, and combinations of each. Products were applied over 13 weeks at Clemson University horticulture greenhouses with samples taken at thatch depth, 0-5.1 cm below thatch, and 5.1-10.2 cm below thatch at conclusion of study. Average Cu concentrations in thatch layer was 634.7 kg Cu ha-1, with 0 - 5.1 cm and 5.1 - 10.2 cm depth concentrations of 11.26 and 6.84 kg Cu ha-1, respectively. Remediation studies exposed 5 mg Cecil sandy loam to 15 ml 1000 ppm of CuSo4-Cu followed by 4 sequential 20 ml filtration cycles of 1 N ammonium sulfate, 1 N calcium nitrate, 1 N gypsum, or water. Single filtration of ammonium sulfate removed similar or greater amount of Cu than cumulative impact of 4 filtrations of any other products with 2064 mg Cu kg-1. Studies suggest that the management or removal of thatch may alleviate toxic accumulation of copper, however the use of ammonium sulfate in irrigation water may provide additional remediation options to turfgrass managers.

Lignins and Lignin Derivatives as Dispersants for Copper Phthalocyanine Pigment Nanoparticles

Copper phthalocyanine (CuPc) is a widely used organic blue pigment with color brilliance, light fastness, and low cost. However, its poor dispersibility in aqueous solutions limits the water-borne application. Lignin’s hyperbranched polymer structure makes it a potential dispersant. In this study, lignin is functionalized with carboxylic acid (−COOH) and amine (−NH2) to enhance the interaction with aqueous solutions. Their applications as dispersants for CuPc in aqueous solutions are investigated together with commercially available alkali lignin, dealkali lignin, and lignosulfonate. The effectiveness of dispersion stability is evaluated by the suspension stability. Lignin-NH2 enhanced the suspension stability of CuPc to allow 94 wt % CuPc particles to remain suspended in water for 24 h compared to 24.4 wt % with no dispersant added. The mechanism of dispersion is revealed by the measurements of zeta potential and particle size, as well as the calculation of lignin adsorption amount on CuPc. Moreover, the lignins are applied to disperse CuPc in acrylic resin as a water-based paint application. With the aid of lignin-NH2 dispersant, CuPc enhances the tinting strength to 110.75% without altering the blue color through color difference measurements. Lignin-NH2 contributes to both better suspension stability and tinting strength than a commercially available dispersant dioctyl sodium sulfosuccinate (DOSS).

Subterranean transport of microplastics as evidenced in karst springs and their characterization using Raman spectroscopy

The increasing use of plastic materials has led to accumulation of large amounts of plastic waste in environment and a global challenge to be tackled with. The natural process of macro-plastics aging generates a multitude of secondary microplastic fragments accumulating in all areas of the planet. The pollution with microplastics of large water bodies, such as rivers, seas and oceans was already proven, but the presence of microplastics even in karst spring water was not reported yet. In this study, Raman micro-spectroscopy was used to confirm the presence of microplastics in the spring water samples collected from two rural karst springs in the Apuseni Mountains (Țarina and Josani), North-Western Romania. Two sets of water samples of 1000 L collected in spring time 2021 and one in autumn 2021 were filtered and analyzed. Using the Python programming language and combining two separate Raman databases, one for plastics and the other for pigments, we established a customized database to unambiguously identify the type of plastic and pigment present in the discovered micro-fragments. The generated reference pigment-plastic spectra were compared to those of potential microplastics found on filters and Pearson's coefficient was used to measure the level of similarity. The presence of microplastics in karst spring waters was confirmed and a quantitative estimation expressed as number of fragments or fibers per liter was 0.034 in Josani and 0.06 in Țarina karst spring. Five months later sampling (autumn 2021) revealed 0.05 microplastics per liter. The spectral results revealed that most microplastics found were dominated by polyethylene terephthalate (PET), followed by polypropylene and interestingly, abundant blue micro-fragments were identified according to their copper phthalocyanine pigments (pigment Blue 15) or indigo carmine (pigment Blue 63) characteristic spectral fingerprints, which surpassed the inherent spectral background level characteristic for the Raman spectra of naturally contaminated waste micro-samples. Their origin in mountain karst spring waters and potential decrease in time is discussed.

Investigation of phthalocyanine diamidophosphate-nickel by thermal analysis

The article presents the results of a study of the synthesis of a new type of pigment - nickel phthalocyanine diphosphate (DAPNiPc), which contains macroheterocyclic compounds. The influence of the method of obtaining a pigment in the liquid and solid phases on its physicochemical properties and intensity has been studied. The gross formula of the pigment is given and the areas of its practical application are shown. Thermal analysis on a Setaram LabSys Evo instrument (France) was used to study the thermal stability of a highly intense pigment of the organic nickel phthalocyanine pigment, which was compared with the closest analog, the copper phthalocyanine pigment. Thermal studies of exothermic and endothermic processes were carried out in the temperature range of 100-500 °C. The results of the mass loss of the pigment upon heating are presented. It is shown that, due to the content of phosphorus-containing compounds, the synthesized pigment has high heat resistance and intensity.

Concentration effect on the optical properties of laser irradiation copper phthalocyanine (CuPc blue) solution

The work aims to study the effect of varying the concentrations on the optical properties of the organic copper phthalocyanine pigment before and after exposure to a laser beam of different wavelengths . The pigment was dissolved in chloroform solvent at room temperature and in several concentrations . The optical properties including the spectrum of absorbance, transmittance, and reflectivity are measured. The work also presents the energy gap data that was calculated from the Tauc equation for all concentrations. The results showed that the band gap decreases with increasing solution concentration. The band gap is measured using both Tauc and fluorescence method, and the values are compared at concentration . The optical parameters such as absorption coefficient, extinction coefficients, refractive index, dielectric constants, and optical conductivity are increased with increasing laser time irradiation for all solution concentrations.

Dispersion of copper phthalocyanine pigment nanoparticles by eco-friendly ethoxylated cardanol in aqueous solution

Abstract The environmentally friendly surfactant ethoxylated cardanol (EC) was investigated for dispersing copper phthalocyanine (CuPc) pigment nanoparticles into aqueous solution. The stability of the dispersion was investigated using UV-Vis spectra. The particle size was measured by optical microscopy, transmission electron microscopy and dynamic light scattering. The surface of the nanoparticles was characterised by measurements of the zeta potential and wettability. The coating application was investigated by incorporating CuPc blue pigment into resin and inorganic filler, and the colour strength of the coating film was compared. The results show that the EC can effectively wet and disperse the CuPc particles. The stabilisation of the particles is achieved by a steric mechanism in which the hydrophobic chains of the surfactant are adsorbed onto the surfaces of the CuPc nanoparticles and the ethylene oxide chains are dispersed in the aqueous phase. At EC concentrations greater than 0.1%, the CuPc nanoparticles appear to deagglomerate. The colour strength of CuPc nanoparticles present as dispersed pigment in resin can be increased in the presence of the EC surfactant.

A Novel Modification of Copper (II) Phthalocyanine Particles towards Electrophoretic Displays.

Electrophoretic display (EPD) is a popular display technology in recent years. The core of the EPD is electrophoretic particles, and its Zeta potential has an important impact on EPDs. In this work, a method using pyrrolidine mono ionic liquid was proposed to improve the Zeta potential of electrophoretic particles: Copper (II) phthalocyanine pigment was modified with mono ionic liquid 1-Butyl-1-methylpyrrolidinium bromide. The characterization results show that the mono ionic liquid had been successfully coated on pigment particles. At the same time, the dispersion and stability of particles were improved. The modified Copper (II) phthalocyanine pigment could be stably dispersed in tetrachloroethylene for more than 20 days. The Zeta potential increased from 32.42 mV to 49.91 mV, increasing by 53.95%. Finally, the prepared blue electrophoretic particles were compounded with white titanium dioxide to prepare blue and white dual-color electrophoretic dispersion, and then an EPD cell was designed to test its performance. The results show that the prepared electrophoretic dispersion can realize reversible reciprocating motion. Therefore, because of the unique structure and properties of pyrrolidine mono ionic liquids, the blue nanoparticles prepared with pyrrolidine ionic liquids as charge control agents in this study can be used as excellent candidate materials for EPD.

Enhanced Solar Reflectance and Superhydrophobic Properties of Functionalized Silica-Coated Copper Phthalocyanine Pigments by the Sol-Gel Process.

This research studies the physical, superhydrophobic, and optical properties of functionalized silica-coated copper phthalocyanine (CuPc) pigments. The silica coating was confirmed by the size increase and the atomic ratio of silicon and copper of the coated pigments. Under optimal conditions, the green and blue shades of the pigments were enhanced as indicated by the increase in solar reflectance at 450–540 nm for the CuPc green and 380–520 nm for the CuPc blue. The total near-infrared (NIR) reflectance of the CuPc green and blue also increases by 10.6 and 11.5% compared to the uncoated pigments, respectively. The functionalized silica layer also adds a superhydrophobic property to the pigments. The contact angles of the functionalized pigments with water and oil are 154.4 and 54.3° for the CuPc green pigment and 142.9 and 78.1° for the CuPc blue pigment, respectively. The improved optical and hydrophobic properties make the pigment suitable for outdoor applications as an advanced protection layer to slow down material degradations from heat and humidity.

Phthalocyanine pigments: general principles

Abstract This chapter describes some of the fundamental chemical and structural principles underlying the phthalocyanine system. Historically, phthalocyanines had been isolated as insoluble blue products in the early twentieth century, although the structures were not established at the time. After the serendipitous re-discovery of metal complex phthalocyanines by industry, and the elucidation of their structures, copper phthalocyanine (CuPc) pigments were introduced industrially in the 1930s to become, and remain, by far the most important blue and green organic pigments, finding almost universal use as colorants for paints, printing inks, plastics, and a wide range of other applications. The phthalocyanines have become one of the most extensively studied classes of organic compounds, because of their unique molecular structures, light absorption properties that produce strong, bright colors, and their exceptionally high stability. While their dominant use is as colorants, they are also of interest for a range of other applications, for example in electronic devices, biological applications, and as catalysts.

Dispersant effect of degraded cellulase and SDS on copper(II) phthalocyanine pigment

The dispersion effect of degraded cellulase from Bacillus methlylotrophicus Y37 and sodium dodecyl sulphate (SDS) together on copper(II) phthalocyanine (CuPc) pigment is studied for the first time in this study. Particle size distribution is used to determine the effect of degradation time for cellulase (1,2,3,4,5,6 and 7 hours). Spectral analysis as UV-Vis, fluorescence, and particle size analysis are investigated to find out the degraded degree of the enzyme. For this work, 4 hours is found to be the optimum degradation time. The collaborative effect of SDS with degraded cellulase as dispersant on CuPc is also examined. The effect of degraded cellulase: SDS dispersion solution on CuPc suspension is determined by UV-Vis, fluorescence, and FT–IR analysis. It is concluded that CuPc has better stability as a pigment when the degraded cellulase and SDS are used together as dispersants in this work.

Spectral Characterization of Argentine Postage Stamps Using Complementary In Situ and Non-invasive Techniques

ABSTRACT This work studies the different materials used in the production of Argentine postage stamps from 1888 to 2016 and explains how the use of these materials has changed over time, thus contributing to knowledge of the national philatelic heritage. Analyses of more than 40 Argentine postage stamps were carried out non-invasively in situ without the need for prior preparation, using portable X-ray fluorescence spectroscopy (p-XRF) and Fourier transform infrared spectroscopy with attenuated total reflectance (FTIR-ATR). Paper, ink, coatings, and adhesives were analysed and the period of use of each material was established. Some notable results include the continuous use of Prussian blue until its replacement by an organic copper phthalocyanine pigment. In addition, it was possible to establish the substitution date of gum arabic as an adhesive by PVA. In general, the variation of the materials used was accompanied by changes in printing techniques. This is the first time that information on the materiality of these historical-artistic objects is published, contributing to the knowledge and conservation of the philatelic heritage of the Argentine Republic.

A novel and low-cost CuPc@C catalyst derived from the compounds of sunflower straw and copper phthalocyanine pigment for oxygen reduction reaction.

A series of carbon and phthalocyanine catalysts were prepared with uniform and stretchable sunflower straw biological materials as the carbon source and inexpensive copper phthalocyanine (CuPc) pigment as a nitrogen doping source by a facile high-temperature carbonization method. This kind of biomass carbon material sunflower straw with abundant pore structure and sponge-like expansion and contraction functions can not only be used as a source of porous carbon in biomass carbon materials, but also as a carbon carrier with high specific surface area to provide nanoparticle adhesion sites. When it was immersed in the copper phthalocyanine pigment solution, more active sites could be exposed, so that CuPc particles could be uniformly doped and distributed on the porous carbon material. As a result, thanks to the doping of nitrogen atoms and the improvement of graphitization degree, the composite catalyst treated at 800 °C (CuPc@C-800) exhibits a porous structure with a 38 mV lower on-set potential and a high stability of 87.4% compared to commercial Pt/C (20%) catalyst. These results demonstrate that CuPc@C series composite catalysts have a splendid electrochemical performance in oxygen reduction reaction catalysts, which can start a new direction for later workers to study combining the properties of biomass carbon material and the phthalocyanine series of catalysts.

Investigating the synergetic dispersing effect of hydrolyzed biomacromolecule Cellulase and SDS on CuPc pigment

In this paper, the dispersion performance of biomacromolecule hydrolyzed cellulase from Trichoderma reesei on copper phthalocyanine (CuPc) pigment was first studied. The effect of hydrolysis time, cellulase concentration and environmental pH on the dispersion performance was investigated by particle size distribution and suspension transmittance measurement. The hydrolysis degree of cellulase was determined by FTIR, XRD, UV–vis and fluorescence spectra, potential and particle size analysis, respectively. Subsequently, the hydrolyzed cellulase was combined with sodium dodecyl sulfate (SDS) for acquiring better CuPc suspension based on their synergetic effects on dispersion. The optimal mass ratio of hydrolyzed cellulase to SDS was found to be 1:9. The resulting CuPc dispersion by this hydrolyzed cellulase/SDS composite was characterized by FTIR, TG, TEM, XRD analysis, respectively. This study demonstrated that there were strong interactions between hydrolyzed cellulase and SDS to result in synergistic dispersing effect on CuPc for better stability.

Sonophotocatalytic oxidation based treatment of phthalocyanine pigment containing industrial wastewater intensified using oxidising agents

In the present study, a novel treatment method based on the combination of ultrasonic and ultraviolet irradiation as well as various additives i.e. oxidants and catalysts has been developed for the treatment of real industrial wastewater containing copper phthalocyanine pigment. The progress of the treatment of wastewater has been monitored in terms of reduction in the chemical oxygen demand (COD), total organic content (TOC) and total dissolved salts (TDS) content. Initially, the effect of operating conditions as ultrasonic power, temperature and pH on the extent of COD reduction has been studied. The optimized conditions established were 100 W as the ultrasound power, pH of 2, temperature of 31 ± 2 °C and reaction time of 120 min. Under these optimized conditions, the combination with photocatalytic oxidation (involving CuO and TiO2) with or without various additives like H2O2 and ozone has been studied. The efficacy of combined approaches was generally higher than individual treatment methods of sonolysis (51.52% as the COD reduction) and photolysis (45.65% as the COD reduction). The actual extent of COD reduction obtained for combined approaches of US/UV/CuO, US/UV/TiO2, US/UV/CuO/O3 and US/UV/TiO2/O3 was 78.5%, 85.5%, 91.67% and 94.44% respectively in 120 min of treatment. Sonophotocatalysis (catalyst as TiO2) combined with ozone established as the most efficient hybrid technique for COD reduction also resulted in maximum TOC removal of 89.17% and TDS removal of 75.74%. Overall, the combination of US + UV + TiO2 + O3 has been established as the most efficient technique for the treatment of phthalocyanine pigment based industrial wastewater, yielding final effluent conforming to discharge standards.

INVESTIGATION OF AN AMPHIPOLAR COPOLYMER ADSORPTION ON THE HYDROPHOBIC SURFACE OF COPPER PHTHALOCYANINE NANOPARTICLES

It was presented the data on the thicknesses of the adsorbed polymer layer, which were obtained for copper phthalocyanine (CuPc) pigment dispersions under ultrasonic processing conditions. The thicker adsorption layers, which are observed in ultrasound systems, confirm the fact that the activation of the surface of the pigment occurs under the action of ultrasonic energy. The course and efficiency of adsorption of the polymer onto the pigment surface were quantified by electrokinetic measurements of the amplitude of sound (EIAZ). It became possible to obtain a more detailed picture of the pigment-polymer interactions and the adsorption mechanism of the copolymer based on the data on the dynamic mobility, obtained as a result of electrokinetic measurements of the amplitude of the sound. For aqueous dispersions of CuPc, stabilized with a copolymer of poly (acrylic acid) -poly (isobornyl acrylate) (PiBA-PAA), it was established the saturation concentrations of polymeric surfactant. Thus, the ultrasonic treatment allows to obtain stable, highly dispersed pigment suspensions with a modified pigment surface, which opens up new prospects for a more effective change in the surface of the pigment.

Lack of evidence for microplastic contamination in honey

ABSTRACTHoney samples from Switzerland were investigated with regard to their microplastic particle burden. Five representative honey samples of different origin were processed following a standardized protocol to separate plastic-based microparticles from particles of natural origin, such as pollen, propolis, wax, and bee-related debris. The procedure was optimized to minimize post-sampling microplastic cross-contamination in the laboratory. The isolated microplastic particles were characterized and grouped by means of light microscopy as well as chemically characterized by microscopically coupled Raman and Fourier transform infrared spectroscopy. Five particle classes with an abundance significantly above blank levels were identified: black particles (particle count between 1760/kg and 8680/kg), white transparent fibres (particle count between 132/kg and 728/kg), white transparent particles (particle count between 60/kg and 172/kg), coloured fibres (particle count between 32/kg and 108/kg), and coloured particles (particle count between 8/kg and 64/kg). The black particles, which represented the majority of particles, were identified as char or soot and most probably originated from the use of smokers, a widespread practice in beekeeping. The majority of fibres were identified as cellulose or polyethylene terephthalate and were most likely of textile origin. In addition to these particle and fibre groups lower numbers of fragments were detected that were related to glass, polysaccharides or chitin, and few bluish particles contained copper phthalocyanine pigment. We found no indications that the honey samples were significantly contaminated with microplastic particles.

The modification of cotton substrate using chitosan for improving its dyeability towards anionic microencapsulated nano-pigment particles

The cotton samples were treated by chitosan solution at acidic condition to modify their dyeing properties to anionic coloring materials. By fluorescence spectrum together with FTIR, XRD and TGA analysis, it was concluded that the chitosan molecules could spontaneous transfer from solution onto cotton surface yet would not influence its internal structure. In order to color the chitosan-treated cotton, an anionic polystyrene-encapsulated copper phthalocyanine (CuPc) pigment was prepared in a miniemulsion process. The full encapsulation of nano-pigment could be directly observed by TEM. The encapsulation would not alter the crystal structure and color properties of CuPc while could make the nano-pigment more stable against centrifuge and temperature variation. Finally, the dyeing properties of this encapsulated nano-pigment on chitosan-treated cotton samples were studied. It was indicated the chitosan molecules on cotton had great capability to improve the uptake of encapsulated nano-pigment mainly due to the accessible amino groups introduced.

RAMAN IDENTIFICATION OF PIGMENTS IN THE WORK OF THE CHILEAN CONTEMPORARY VISUAL ARTIST IGNACIO GUMUCIO

The main pigments in the painting by the Chilean artist Ignacio Gumucio were identified by using micro-Raman spectroscopy. Three works by the artist, two paintings with wooden stand and a wall painting were analyzed. Pigments were vibrationally identified from cross-section samples of the contemporary paints on wood Rio and Saludo and the wall painting Mental. The blue color Raman bands corresponds to cooper phthalocyanine. In the green areas, the Raman signals were ascribed to the azopigment acetoacetic arylide and copper phthalocyanine; the green color is then the result of a combination of the yellow and blue pigments. Raman bands in the pink areas were assigned to the azopigment β-naphthol. The dark green color in the Saludo paint is due to a chlorinated copper phthalocyanine pigment. Other materials in the artworks were also identified: rutile (TiO2) in Saludo in white areas and calcite (CaCO3) in Mental and Rio. On this basis and taking into account the identification of the state of conservation a protocol for the preservation of the artworks Rio and Saludo can be assessed.

Pyrolysis gas chromatography mass spectrometry of two green phthalocyanine pigments and their identification in paint systems

Copper phthalocyanine pigments are commonly used in modern paints, printing inks, plastics, leather, and synthetic fibres. Here, a systematic pyrolysis/gas chromatography–mass spectrometry study of two commonly used green copper phthalocyanine pigments (PG7 and PG36) was carried out. Pyrolysis temperatures ranging from 300°C up to 800°C were applied in order to study the pyrolysis products generated at each temperature. At temperatures above 700°C very volatile products such as ClCN—for PG7 – and HBr, CH3Br and BrCN—for PG36 – were relatively abundant, whereas at higher retention times a series of halogenated aromatic compounds could be identified.Py/GC–MS of green acrylic and oil paint systems containing PG7 and PG36 was also performed in order to verify the possibility to detect low amounts of copper phthalocyanine pigments in complex matrices. Although not all the pyrolysis products of the reference green copper phthalocyanine pigments could be detected, efficient identification of these pigments could be accomplished thanks to the presence of specific markers.

Durable and flexible graphene composites based on artists’ paint for conductive paper applications

An acrylic emulsion artists’ paint containing chlorinated copper phthalocyanine pigment was modified with variable-size multilayer graphene (exfoliated graphite) to induce low electrical resistance; composite films were spray-cast on common printing paper, heat-cured, and subsequently polished under mild compression, to produce highly conductive paper. The mechanically robust conductive paint showed excellent adhesion to the underlying paper, as determined by Taber abrasion and tape peel tests, which displayed no adhesive failure under the test conditions studied. The conductivity of the paper substrates were tuned by changing the concentration and the size of the multilayer graphene particles. Detailed conductivity measurements showed stable Ohmic current–voltage behavior. The optimum graphene-in-paint formulations resulted in sheet resistances of the order of 10Ω/sq. Standard electrostatic force microscopy measurements showed uniform surface electric field gradient distribution strongly correlating with the surface topography. Similarly, scanning Kelvin probe microscopy measurements indicated stable work functions close to 5eV, comparable to highly-ordered pyrolytic graphite. Furthermore, Kelvin probe measurements were more sensitive to surface charges related to copper phthalocyanine domains, which are known to have semiconducting properties. Finally, the conductive papers were also tested in the 0.50–0.75 terahertz frequency range for electromagnetic interference shielding (EMI) characterization and displayed quasi-metallic shielding performance.