Effect of low molecular weight organic acids on the lead and chromium release from widely-used lead chromate pigments under sunlight irradiation.

Lead chromate pigments are commonly used yellow inorganic pigments. They can pose environmental risks as they contain toxic heavy metals lead and chromium. Low molecular weight organic acids (LMWOAs), as widespread dissolved organic matter (DOM), affect the lead and chromium release from the pigment in water. In this work, the role of LMWOAs in the photodissolution of commercial lead chromate pigment was investigated. The pigment underwent significant photodissolution under simulated sunlight exposure with LMWOAs, and subsequently released Cr(III) and Pb(II). The photodissolution process is caused by the reduction of Cr(VI) by photogenerated electrons of the lead chromate pigment. The LMWOAs promoted photodissolution of the pigment by improving the electron-hole separation. The formation of Cr(III)-contained compounds leads to a slower release of chromium than lead. The photodissolution kinetics increase with decreasing pH and increasing LMWOAs concentration. The photodissolution of lead chromate pigment was basically positively related to the total number of hydroxyl and carboxyl groups in LMWOAs. The LMWOAs with stronger affinity to lead chromate pigment, lower adiabatic ionization potential (AIP) and higher energy of the highest occupied molecular orbital (EHOMO) are favorable to Cr(VI) reduction by photogenerated electrons and pigment photodissolution. 2.39% of chromium and 10.34% of lead released from the lead chromate pigment in natural conditions during a 6-h sunlight exposure. This study revealed the photodissolution mechanism of lead chromate pigment mediated by LMWOAs with different molecular structures, which helps understand the environmental photochemical behavior of the pigment. The present results emphasize the important role of DOM in the heavy metals release from commercial inorganic pigments.

Synthesis of Cobalt-Substituted Manganese Phosphate Purple Pigments.

Some manganese phosphates are known as violet pigments. In this study, pigments in which manganese was partially replaced with cobalt and aluminum was replaced with lanthanum and cerium were synthesized with a heating method to obtain pigments with a more reddish color. The obtained samples were evaluated in terms of chemical composition, hue, acid and base resistances, and hiding power. Among the samples examined, the samples obtained in the Co/Mn/La/P system were the most vivid. The brighter and redder samples were obtained by prolonged heating. Furthermore, prolonged heating improved the acid and base resistance of the samples. Finally, the substitution of manganese for cobalt improved the hiding power.

Preparation and Chromaticity Control of CoTiO3/NiTiO3 Co-Coated TiO2 Composite Pigments.

In this study, home-made amorphous TiO2 microspheres with good mono-dispersity and large numbers of mesopores on the surface were used as substrates. The intermediate microspheres were obtained by adding Co/Ni sources with different Co/Ni molar ratios in a water bath and making them react by water bath heating. By calcining the intermediate microspheres deposited on the TiO2 ones, a core-shell structured spherical CoTiO3/NiTiO3 inorganic composite pigment was prepared. The synthesized pigments were characterized by X-ray diffraction (XRD), Raman spectroscopy, field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectrometry (EDS), laser particle size (LPS) analysis and colorimetry. The results show that when the calcination temperature is 800 °C and the Co/Ni molar ratio is 0.5:0.5, the pigments consist of a TiO2 core and outer ilmenite CoTiO3/NiTiO3 shell. Moreover, the surface of the product microspheres is smooth, and the particles are of regular sphericity with a uniform particle size of about 1.8 µm. The colorimetric analysis from the samples calcined at 800 °C shows color changes from yellow-green to dark green as the Co/Ni molar ratio increases (0.1:0.9 to 0.9:0.1). A Co/Ni molar ratio that is too high or too low results in the formation of by-products such as Co3O4 or NiO, respectively, which adhere to the product surface and affect the chromaticity of the product. This work has enabled the chromatic modulation of yellow-green inorganic pigments, providing a solution for the preparation of spherical inorganic pigments that are more suitable for industrial inkjet printing.

Treatment of galvanic effluent through electrocoagulation process: Cr, Cu, Mn, Ni removal and reuse of sludge generated as inorganic pigment.

Galvanic effluents are composed of a wide range of heavy metals, requiring adequate treatment to remove these contaminants and to meet the limits established by environmental agencies. Considering this aspect, the present study had as main objectives: (i) to evaluate the efficiency of the electrocoagulation (EC) in the treatment of a galvanic effluent, with the purpose of removing total Cr, Cu, Mn, Ni and (ii) reuse the sludge generated for inorganic pigment production. EC tests were carried out through factorial design 23 with triplicate central point. pH (3, 7, 11), reaction time (15, 22.5 and 30 min) and current density (10, 17.5 and 25 mA/cm2) were the control variables. Under ideal experimental conditions (pH 7.00; t = 22.5 min and DC = 17.5 mA/cm2) were removed 96.94% of Mn, 97.63% of Cu and 99.99% of total Cr and Ni, allowing to meet the limits provided in CONAMA Resolution 430/2011. The production of inorganic pigments from a mixture of 10% sludge (generated in the ideal experimental condition) and Al2O3 and TiO2 proved to be technically viable. It was obtained 8.27 g of a brown inorganic pigment, composed mainly of Al1.82Cr0.18O3, Ca0.999(Ti0.805Fe0.201)O2.899 and Fe2.18O4Ti0.42. Therefore, the results obtained demonstrate that EC is an effective technique in galvanic effluents treatment. The sludge generated in this process showed to be appropriated to be reused in inorganic pigment production and could be considered as an alternative to reduce the environmental impact related to electroplating process.

Automated Inorganic Pigment Classification in Plastic Material Using Terahertz Spectroscopy.

This paper presents an automatic classification of plastic material's inorganic pigment using terahertz spectroscopy and convolutional neural networks (CNN). The plastic materials were placed between the THz transmitter and receiver, and the acquired THz signals were classified using a supervised learning approach. A THz frequency band between 0.1-1.2 THz produced a one-dimensional (1D) vector that is almost impossible to classify directly using supervised learning. This paper proposes a novel pre-processing of 1D THz data that transforms 1D data into 2D data, which are processed efficiently using a convolutional neural network. The proposed pre-processing algorithm consists of four steps: peak detection, envelope extraction, and a down-sampling procedure. The last main step introduces the windowing with spectrum dilatation that reorders 1D data into 2D data that can be considered as an image. The spectrum dilation techniques ensure the classifier's robustness by suppressing measurement bias, reducing the complexity of the THz dataset with negligible loss of accuracy, and speeding up the network classification. The experimental results showed that the proposed approach achieved high accuracy using a CNN classifier, and outperforms 1D classification of THz data using support vector machine, naive Bayes, and other popular classification algorithms.

High-Quality Inorganic Red Pigment Prepared by Aluminum Deposition on Biogenous Iron Oxide Sheaths.

Naturally occurring tubular iron oxides produced by aquatic bacteria in Leptothrix spp. are promising raw materials for hematite-based red pigments because of the higher heat resistance as compared with chemically synthesized hematite compounds. Here, we report iron oxide red pigments prepared through an additive deposition of aluminum on culture-based biogenous iron oxide (cBIOX) sheaths using an artificial culture system of L. cholodnii strain OUMS1. The heat-treated Al-containing cBIOXs exhibited elevated chroma and lightness along with increasing Al contents and enhanced thermal stability of color tones to repetitive heat treatments. XRD analysis showed a monophasic pattern of hematite in the Al-rich cBIOX after heating at a wide range of high temperatures. Micromorphology analyses revealed that putative Al oxide regions present among hematite particles plausibly prevented the grain growth of hematite during heat treatments. The results therefore demonstrate that the bioderived Al-rich iron oxide sheaths can serve as innovative inorganic red pigments feasible for industrial applications.

Smart textile framework: Photochromic and fluorescent cellulosic fabric printed by strontium aluminate pigment.

Smart clothing can be defined as textiles that respond to a certain stimulus accompanied by a change in their properties. A specific class herein is the photochromic and fluorescent textiles that change color with light. A photochromic and fluorescent cotton fabric based on pigment printing is obtained. Such fabric is prepared by aqueous-based pigment-binder printing formulation containing inorganic pigment phosphor characterized by good photo- and thermal stability. It exhibits optimal excitation wavelength (365 nm) results in color and fluorescence change of the fabric surface. To prepare the transparent pigment-binder composite film, the phosphor pigment must be well-dispersed via physical immobilization without their aggregation. The pigment-binder paste is applied successfully onto cotton fabric using screen printing technique followed by thermal fixation. After screen-printing, a homogenous photochromic film is assembled on a cotton substrate surface, which represents substantial greenish-yellow color development as indicated by CIE Lab color space measurements under ultraviolet light, even at a pigment concentration of 0.08 wt% of the printing paste. The photochromic cotton fabric exhibit three excitation peaks at 272, 325 and 365 nm and three emission peaks at 418, 495 and 520 nm. The fluorescent optical microscope, scanning electron microscope, elemental mapping, energy dispersive X-ray spectroscopy, fluorescence emission and UV/Vis absorption spectroscopic data of the printed cotton fabric are described. The printed fabric showed a reversible and rapid photochromic response during ultra-violet excitation without fatigue. The fastness properties including washing, crocking, perspiration, sublimation/heat, and light are described.

Avaliação da utilização das cinzas da escuma gerada em Reator Anaeróbico de Manta de Lodo e Fluxo Ascendente como pigmento inorgânico de coloração alaranjada / Evaluation of the use of ashes of scum generated from the Upflow Anaerobic Sludge Blanket reactor as orange inorganic pigment

RESUMO A escuma é um resíduo gerado durante o tratamento anaeróbico de efluentes domésticos que necessita de periódica remoção para não comprometer a eficiência do processo. O presente trabalho teve por objetivo utilizar as cinzas da escuma gerada em Reator Anaeróbico de Manta de Lodo e Fluxo Ascendente (RALF) como pigmentos inorgânicos. Amostras de escumas coletadas em diferentes meses foram submetidas a tratamento térmico a 900°C por 1h para remoção da matéria orgânica. As cinzas obtidas foram desaglomeradas em peneira e submetidas às análises química (Fluorescência de raios X - FRX), mineralógica (Difração de raios X - DRX), morfológica (Microscopia Eletrônica de Varredura por Efeito de Campo - FE-MEV) e de coloração (espectroscopia de reflectância difusa na região do Ultravioleta-Visível - UV-Vis). As amostras apresentaram composição majoritária de elementos comuns no ambiente, sendo as fases principais identificadas o quartzo (dióxido de silício - SiO2), a anidrita (sulfato de cálcio - CaSO4) e a hematita (óxido de ferro - Fe2O3). A granulometria das amostras é adequada para a aplicação como pigmento cerâmico; a coloração obtida foi alaranjada intensa e boas propriedades foram identificadas, como boa opacidade, omitindo a coloração do suporte cerâmico, além de não existirem defeitos superficiais que indicassem matéria orgânica residual ou incompatibilidade com o esmalte utilizado. Sendo assim, as cinzas da escuma gerada em RALF apresentaram características interessantes para a aplicação como pigmentos cerâmicos.

ABSTRACT Scum is a residue generated during the anaerobic treatment of domestic effluents and requires periodical removal in order not to harm the process efficacy. This study aimed to use the scum ashes generated from Upflow Anaerobic Sludge Blanket (UASB) reactor as inorganic pigments. The scum samples collected in different months were thermally treated at 900°C for one hour for removal of organic matter. These ashes were dispersed and submitted to chemical (X-ray Fluorescence - XRF), mineralogical (X-ray Diffraction - XRD), morphological (Field Emission Scanning Electron Microscopy - FE-SEM) and color (Ultraviolet-Visible Diffuse Reflectance Spectroscopy - UV-Vis DRS) analyses. The samples were composed mainly by elements commonly found in the environment. The main crystalline phases are quartz (silicon dioxide - SiO2), anhydrite (calcium sulfate - CaSO4) and hematite (iron oxide - Fe2O3). Also, these particles presented suitable size for application as ceramic pigment and the color obtained was intense orange. When applied as ceramic pigment at the decorative fire temperature, the enameled piece presented intense color and the pigment had good opacity, hiding the ceramic support color, besides, they presented no surface deformations, which indicates the pigments are compatible with enamel. Thus, scum ashes generated in UASB reactor presented interesting characteristics to be applied as ceramic pigments.