Research into the use of marble waste as mineral filler in soil pigment-based paints and as an active pigment in waterborne paints

Construction and Building Materials 241 (2020) 117976

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Research into the use of marble waste as mineral filler in soil pigment-based paints and as an active pigment in waterborne paints Deise Mara Garcia Alves Tressmann a,⇑, Leonardo Gonçalves Pedroti a, Anôr Fiorini de Carvalho b, José Carlos Lopes Ribeiro a, Fernando de Paula Cardoso a, Márcia Maria Salgado Lopes a, André Fernando de Oliveira c, Sukarno Olavo Ferreira d a

UFV – Federal University of Viçosa, DEC – Civil Engineering Department, Av. Peter Rolfs, s/n, Campus Universitário, 36570-000 Viçosa, Brazil UFV – Federal University of Viçosa, DPS – Soil Department, Av. Peter Rolfs, s/n, Campus Universitário, 36570-000 Viçosa, Brazil UFV – Federal University of Viçosa, DPQ – Chemistry Department, Av. Peter Rolfs, s/n, Campus Universitário, 36570-000 Viçosa, Brazil d UFV – Federal University of Viçosa, DPF – Physics Department, Av. Peter Rolfs, s/n, Campus Universitário, 36570-000 Viçosa, Brazil b c

h i g h l i g h t s
Untreated marble waste used as a pigment in paint to contribute to environment.
Paints made with marble waste as pigment can meet the normative specifications.
The soil pigment-based paint was improved by incorporating MWP as a mineral filler.
MWP contributed to increased paint durability and greater photolytic stability.

a r t i c l e

i n f o

Article history: Received 4 May 2019 Received in revised form 29 November 2019 Accepted 27 December 2019

Keywords: Marble waste Waterborne Sustainable development Soil pigment

a b s t r a c t Producing paint using waste and soil is an efficient way of contributing to sustainable development and reducing costs in the finishing and protection of buildings. Although there are numerous studies related to paints of natural land base, there remain certain technical limitations to be overcome. Moreover, no research has been found in the literature on the use of marble waste as an active or inert pigment in the production of paint, although this waste has several pertinent properties and basic constituents. Thus, the aim of this study was to evaluate whether the use of untreated marble waste as an active pigment in building paint enables a product to be developed which meets specifications and whether the performance of soil pigment-based paints can be improved by incorporating marble waste as a mineral filler. The only preparation for using the waste and the soils as pigments was to sieve them to remove coarser impurities. The samples were formulated based on mix planning using the simplex network and consisted of: marble waste pigment (MWP), soil pigment (SP) and polyvinyl acetate resin (PVA). The amount of water varied according to the ideal viscosity range for paint application. The formulas were analyzed for hiding power (HP), abrasion resistance (AR), microbiological attack and resistance to weathering. The results showed that, for paints produced with MWP as the only pigment, the performance set out in ABNT NBR 15079:2011 was achieved above a percentage of 30% resin in solution. Furthermore, the addition of MWP to SP-based paints provided a film with higher HP and, together with the increased resin content, increased the AR of the samples. Five formulas met both HP and AR performance specifications. The percentages in the mixture were as follows: 0.3 PVA and 0.7 MWP; and 0.4 PVA and 0.6 MWP, with MWP as the sole pigment; 0.25 PVA, 0.175 YSP (yellow soil pigment) and 0.575 MWP; and 0.35 PVA, 0.175 YSP and 0.475 MWP, of YSP and MWP; and 0.25 PVA, 0.175 RSP (red soil pigment) and 0.575 MWP, of RSP and MWP. The weatherability test showed that MWP addition to the paint formula contributed to increased paint durability and improved photolytic stability. Thus, the results indicate that marble waste, as an active pigment or mineral filler, is a promising alternative for producing building paint. Ó 2019 Elsevier Ltd. All rights reserved.

⇑ Corresponding author. E-mail addresses: [email protected], [email protected] (D. M. G. A. Tressmann). https://doi.org/10.1016/j.conbuildmat.2019.117976 0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.

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1. Introduction Economic growth coupled with environmental and social responsibility is a topic increasingly discussed by the various productive sectors and also serves as the basis for a great deal of scientific research. Industrial growth, in particular, has increased the consumption of non-renewable natural resources and even led to the exhaustion of some of them [1]. In addition, much waste is generated and can negatively impact the environment in countless ways. Worldwide production of ornamental and cladding stones totaled 145 million tons in 2017, according to the Brazilian Association of the Ornamental Stones Industry ABIROCHAS [2]. Marble represents 50% of this world production [3]. The volume of refuse generated can reach 50% of the volume of all marble blocks processed, making up millions of tons of waste produced every year. The marble industry is one of the sectors that most produces waste from raw materials [4]. Most of this material is landfilled and has serious potential for environmental contamination and health risks [5]. The construction industry is that with the greatest potential use for marble waste [4]. Studies indicate that this by-product has shown positive results when incorporated into different building materials, such as in bricks [6], cement production [7], concrete [8], paving blocks [9], adhesive mortar [10], masonry blocks [11], high-gloss calcite powder [12], and added to concrete to protect a rebars against corrosion [13], among others. Marble waste also has a basic composition that suggests its applicability as a pigment in paints. According to Awol [7], calcium carbonate (CaCO3) is the most widely-used mineral filler in the production of paints. This component is one of the main constituents of carbonaceous rocks and, therefore, of marble waste. Some properties which calcium carbonate enhances in paints include: brightness, opacity, mechanical characteristics and dispersion stability [14]. Several studies have already been carried out on extracting pure calcium carbonate from marble waste for use as a filler, especially in the paper industry [12,15,16]. In all these cases, however, the process is sophisticated and often involves the emission of greenhouse gases. No studies were found in the literature on the use of untreated marble waste as a pigment for the manufacture of paint. Paint can be considered the most effective industrial product, taking into account the cost-benefit binomial [17]. As a result of the paint curing process, a thin, but solid and adherent film is formed on the substrate, which fulfills several functions, including: substrate protection, finish, decoration, sanitation, reflectivity and distribution of light and heat. However, in a holistic approach to the paint system, considering its useful life, frequency of repainting and its manufacturing process, it is noticed that paint is a product with high economic impact for the user and for the environment, indicating the need for new, more sustainable and low-cost techniques for producing it [18]. In this context, the demand for improved coating systems, specially designed to minimize losses and encourage the recovery and reuse of waste, also increases [19]. Several pieces research have been conducted aiming to evaluate the use of waste in the paint industry. The rejects from several industrial processes have already been studied: copper extraction [20], stainless steel finishing [21], iron silicon and silicon metal production [22], iron ore mining tailings [23] and granite processing [24]. In addition to uses for waste, other solutions have been researched and improved to promote sustainable development. One example is the manufacture of soil pigment-based paints, an abundant raw material with low environmental impact

considering, for example, non-emission of volatile organic compounds (VOCs), which is a major concern for the paint industry [19]. Soil constituents have important characteristics for paint formulas. Iron oxide, for example, present in various types of soil, is widely used in this industry. Natural iron oxide pigments are low cost, have a variety of colors and protect the vehicle from degradation from light and acid and alkali weathering. In some cases this pigment also provides protection against the passage of moisture to the substrate [25]. However, none of the soil pigment-based based paint formulas researched in the literature to date have met Brazilian normative specifications for both hiding power and abrasion resistance, which demonstrates the need for further studies in the area [24,26]. Thus, the aim of this study was to improve the performance of soil pigment-based paints through the use of the marble waste, recovered from the sawing blocks and polishing slabs, as a mineral filler, rather than commercial CaCO3. Furthermore, the aim was to evaluate the feasibility of using marble waste as an active pigment in waterborne paints and, at the same time, meeting the requirements of a social interest technology, so that the production process can be replicated easily. 2. Material and methods 2.1. Materials The paints were made with marble waste and/or soil, water and polyvinyl acetate resin (PVA), with density 1,05 g/cm3 and pH medium 4,50. The factors considered for resin choice were the social benefits, due to their low cost; environmental, as they enable the use of water rather than organic solvents; and technical, such as: good durability, rapid drying, high chemical inertia, as well as flexible films, which enable optimum spreading and leveling [27]. Additives were not used in the manufacture of paints for two reasons: first because of the social and economic character of the research; and second, in order to analyze the effect of the interaction between the resin and the pigments in isolation. The marble waste was collected after primary processing of the rocks by cutting with diamond wire. This material was obtained in the southern region of the state of Espírito Santo, Brazil. Soil was collected in the southeastern region of the state of Minas Gerais, Brazil, due to the availability and representativeness of tones available, one being ochre yellow and the other terracotta red. Moreover, these soils are already used by local people in making paint. To prepare the materials as pigments, the waste and the soils, separately, underwent deagglomeration and manual sieving using an ABNT No. 2 sieve, 2.4 mm aperture, to separate coarse impurities. Then, mechanical dispersion was carried out in a wet medium with the cowles disk coupled to a mechanical mixer, at a speed of 1500 rpm. This equipment is the same used in the preparation of the paint. After stabilization of the vortex of the material, which indicates deflocculation and wetting of the particles in effective dispersion [28], the sieving was carried out in a wet medium using the ASTM 80 mesh sieve, 0.177 mm aperture. The sieve was chosen according to the ease of reproduction of the procedure [26]. 2.2. Pigment characterization The pigments could be characterized physically based on determination of the grain size distribution curve, according to the provisions of ABNT NBR 7181 [29]; with the definition of the specific surface, through the BET adsorption method (Brunauer, Emmett and Teller), using Quantachrome NOVA 2200 equipment; according to the determination of the density of particles, according to

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Embrapa [30]; and the percentage of organic matter using the modified Walkley-Black method [31]. For the chemical characterization X-ray fluorescence was performed using the Shimadzu EDX-700 equipment; and pH was obtained according to Embrapa guidelines [30]. For mineralogical characterization, X-ray diffraction was carried out using the X’Pert Pro MPD diffractometer. Scanning electron microscopy (SEM) was performed using Leo 1430VP equipment and enabled morphological characterization of the pigments. 2.3. Experimental model The paint formulas were defined based on a simplex network ternary mix design, with an extreme vertex design for a grade 3 polynomial, including the axial and central points. The marble waste pigment (MWP), soil pigment (SP) and resin (PVA) were the independent variables. The proportions and ranges of the paint components were determined based on recommendations in the literature for PVA latex paints. The main references used were studies by Lambourne and Strivens [32], Greiner et al. [33], Silva and Uemoto [34] and Fazenda [17]. Thus, the pigments had variations from 0% to 80%, relative to the total solids, and the resin from 20% to 40%, considering resin at 50% dilution, as commercially acquired. Another factor considered in the proportion of the constituents of the paint was PVC (pigment volume concentration) [28,35]. PVC is obtained by the ratio between the volume of pigments (active and inert) and the total solids volume of the dry film. In the paint formula studied, PVC varied from 54 to 82%. The experiment design was defined using the MinitabÒ software 17, as shown in Table 1 and Fig. 1, and was reproduced twice, once for yellow soil pigments (YSP) and again for red soil pigments (RSP). To prepare the paints, the amounts of pigments in aqueous environment were mixed with PVA resin considering the pigment and resin mass ratios of Table 1. The amount of water in the formulas was defined in order to achieve desirable application characteristics corresponding to conventional paint. In this way, the ideal flow time of 14 ± 1 s could be achieved, measured by the Ford cup number viscometer orifice number 4, according to ABNT NBR 5849 [36]. 2.4. Paint sample production, characterization and performance The production process was divided into three basic steps: premix; weighing and dispersion; supplementation and dispersion. For premixing the pigment solution, the cowles disk coupled to a mechanical mixer was used for 30 min at 1,500 rpm. Subsequently, the material was weighed and the solids content corrected with the addition of water. For this mixture, dispersion occurred at a speed of 400 rpm for 10 min. In the next step the resin mix was supplemented and the pigment dispersion in the medium with Table 1 Paint formula defined using MinitabÒ statistical software 17. Sample

PVA Resin

Soil Pigment

Marble Waste Pigment

1 2 3 4 5 6 7 8 9 10 11 12 13

0.20 0.30 0.40 0.25 0.35 0.2 0.3 0.4 0.25 0.35 0.2 0.3 0.4

0.8 0.7 0.6 0.575 0.475 0.4 0.35 0.3 0.175 0.175 0 0 0

0 0 0 0.175 0.175 0.4 0.35 0.3 0.575 0.475 0.8 0.7 0.6

Fig. 1. Representation of the combinations between the proportions of the components in the paint formulas: PVA resin (PVA), soil pigment (SP) and marble waste pigment (MWP).

the cowles disk at 300 rpm for 10 min. This step is fundamental because it enables wetting of the particles, stabilization of the medium and prevents pigment flocculation [17]. The viscosity of each sample was tested using the Ford cup viscometer with at least 3 replicates and the solvent added, when necessary, until the flow time of (14 ± 1) s was achieved. The compositions of the paints produced can be seen in Table 2, with respective flow times. The value of the resin is shown in its pure form, that is, considering only the solid fraction. To characterize the samples, the solids content was determined based on ASTM-D 3723-05 [37] specifications and pH using the Digimed pH meter model DM-23. The performance requirements are assessed based on ABNT NBR 15,079 [38]. For paints in the economical latex category, the criteria of interest are: dry paint hiding power (HP) and wet abrasion resistance without abrasive paste (AR). HP was determined according to ABNT NBR 14,942 [39], with methodology similar to ASTM D2805-11 [40] and ISO 6504-3 [41]. The test consists of checking paint yield, measured in square meters per liter (m2/L), capable of providing a dry film with a 98.5% contrast ratio. AR was determined according to ABNT NBR 15,078 [42], with technique similar to ASTM D4060-14 [43] and ISO 7784-3 [44]. The resistant capacity of the paint film is tested by mechanical wear caused by brushing. The result is expressed based on the number of cycles required to remove 80% of the paint film with the brushing process. 2.5. Ideal formulas and statistical analyses After the tests, the results underwent statistical analysis using the MinitabÒ software. Initially the experimental data were adjusted to the complete cubic model and then to the lowergrade models according to significance (p-value < 0.05). The fit of the model was verified according to determination coefficient R2. To outline the optimal regions of the performance parameters, the desirability function was used, based on the simultaneous optimization methodology proposed by Derringer and Suich [45]. Each response variable was given an individual desirability value ranging from zero (unacceptable value) to one (most desirable value). The combination of desirability is found by the simple geometric mean of individual desirability. The performance parameters used were for abrasion (AR) and hiding power (HP), according to the limits established in ABNT NBR 15,079 [38], for economical latex paints.

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Table 2 Composition of paints produced and viscosity. Sample

1 2 3 4 5 6 7 8 9 10 11 12 13

MWP and/or YSP

MWP and/or RSP

YSP (g)

MWP (g)

PR (g)

Water (g)

V (s)

RSP (g)

MWP (g)

PR (g)

Water (g)

V (s)

200.00 200.00 200.00 150.00 150.00 100.00 100.00 100.00 50.00 50.00 0.00 0.00 0.00

0.00 0.00 0.00 45.65 55.26 100.00 100.00 100.00 164.29 135.71 300.00 300.00 300.00

25.00 42.86 66.67 32.61 55.26 25.00 42.86 66.67 35.71 50.00 37.50 64.29 100.00

631.67 652.86 863.58 696.39 741.16 508.44 585.75 694.42 383.95 418.76 235.39 293.99 389.98

13.15 15.12 13.00 14.51 14.89 14.80 14.03 14.03 14.92 14.35 14.97 15.00 15.00

200.00 200.00 200.00 150.00 150.00 100.00 100.00 100.00 50.00 50.00 0.00 0.00 0.00

0.00 0.00 0.00 45.65 55.26 100.00 100.00 100.00 164.29 135.71 300.00 300.00 300.00

25.00 42.86 66.67 32.61 55.26 25.00 42.86 66.67 35.71 50.00 37.50 64.29 100.00

825.00 862.86 926.67 676.83 724.38 500.76 542.15 589.49 365.86 384.23 235.39 293.99 389.98

13.20 14.98 13.29 13.53 14.06 14.48 14.15 14.30 14.61 14.87 14.97 15.00 15.00

YSP – Yellow soil pigment; MWP – Marble waste pigment: RSP – Red soil pigment; PR - Pure resin; V – Viscosity.

2.6. Microscopic analysis The final films of the optimum formulas were evaluated microscopically based on the images and film thickness and roughness. The film images, generated after application and drying of the paint, were obtained using Leo 1430VP scanning electron microscope (SEM). Each paint sample was painted on a three-coat stub, metallized with gold and analyzed on SEM. The thickness and roughness of the films were obtained using the Contour GTK 3D optical profilometer and the images were processed using the Gwyddion software (Gwyddion v2.37; GNU General Public License). The arithmetic mean of the surface roughness, the root mean square of the surface roughness and the thickness of the samples were determined. In analyzing the thickness, excess paint at the edges, inherent in the application of the material, was not considered. 2.7. Paint durability evaluations The paint’s potential for biodeterioration was examined through their predisposition to fungi and bacteria development. The samples subjected to these tests were produced with each type of pigment exclusively, with the highest proportion of the range studied (80% by mass) as, according to Fazenda [17], most contaminants are present in water and in the raw material itself. Serial dilution of the paint samples was performed so that the concentration of microorganisms decreased, giving rise to sufficiently separate colonies, thus enabling them to be counted and isolated. Aliquots of different concentrations were transferred to petri dishes containing potato-dextrose-agar medium (PDA) for fungal growth and in 523 medium [46] for bacteria growth. Subsequently, the dishes were taken to a growth chamber with controlled photoperiod. The PDA dishes were kept at room temperature for 5 days. The fungi were identified by microscopic observations of their structures (conidiophore). Homogeneous bacterial colonies, obtained after 2 days incubation of the dishes at 28 °C, underwent DNA extraction, PCR (Polymerase Chain Reaction) amplification and sequencing of the 16S region. All procedures followed the methodology proposed by Alfenas and Mafia [47]. The paints were also subjected to natural weathering, according to ASTM G7 [48] and ISO 2810 [49], suited to Brazilian reality that included the use of a mortar substrate; application of tree paint coats and the 20° inclination of the frame, as latitude of the exposition place. Simulating conventional uses for latex paint, the samples were applied to a mixed mortar substrate, made of

20 cm  40 cm wood frames and thickness 2,5–3,0 cm, representing the external coating used in buildings. The mixed mortar was produced with cement, lime and sand, trace 1:1:6 by volume. A wire mesh was positioned in the center of the frames to facilitate grout fixation while curing and anchoring. In addition, the wire mesh increases the strength of the mortar panel and decreases its cracking. Three coats of each paint were applied to the substrates without sealer. A drying time of about four hours between coats was used according to weather conditions. In addition to the paint in Table 2 and 3 additional samples were produced on the substrates, produced with pure pigments and without PVA resin, for visual comparison of the results, totaling 26 specimens. The frames were positioned randomly on a fixed panel, oriented so that the paint film received maximum incidence of radiation. The samples also weathered by rain, wind and temperature fluctuations. As the test site in the Southeastern state of Minas Gerais, Brazil, lies at latitude 20° 450 1400 S and longitude 42° 520 0500 W, the structure faced north with a slope of 20° in relation to the vertical. 20 degrees of inclination does not replicate the real situation, but it maximize the sun and rain effects that act in paint pellicle, allowing an evaluation upon this unfavorable scenario exposition. The panels were also partially covered for comparisons and simulations between the internal and external environments, as can be seen in Fig. 2, allowing to evaluate also the possibility of biological growth in this situation. The monitoring took place over a 16-month-period, to evaluate the appearance of pathological manifestations, with regular inspections and photographic record. The results of the visual inspections were compared with the data of solar incidence, temperature and precipitation in the municipality in which the test took place, obtained from the Principal Climatological Station of Viçosa [50,51], located approximately 150 m from the site of the test. After the sixteen-month exposure period, the metal plates were removed. The delta-E (DE) color comparison method was used to compare the results between the applied paint in a protected environment (under the plate) and the external part, subject to weathering. The DE represents the Euclidean distance difference between the spectra of an RGB and is measured from 0 to 100. This method is adopted by the International Commission on Illumination (CIE), because it is that which best approaches color perception by the human eye [23]. PhotoshopÒ software was used to take the readings and the DE value was obtained with the help of Delta-E Calculator software [52]. Besides that, after 72 weeks in the natural weathering exposition, the paint films were again evaluated for biological growth and performance.

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Deise Mara Garcia Alves Tressmann et al. / Construction and Building Materials 241 (2020) 117976 Table 3 Physical and chemical characterization of the pigments. Pigment

Particle density (g/cm3)

Specific surface area (m2/g)

Organic matter (%)

MWP RSP YSP

2.59 2.65 2.46

4.88 48.14 34.55

0.24 0.14 0.36

Granulometry (%) Clay

Silt

Thin sand

12.6 63.8 37.5

74.0 21.9 48.4

13.3 14.3 14.2

Mean Diameter (lm)

pH

15 <1 5.5

8.78 6.18 5.64

MWP – Marble waste pigment: RSP – Red soil pigment; YSP – Yellow soil pigment.

Fig. 2. Weathering resistance trial using 26 boards partially covered with a slab galvanized steel, setted up in a steady panel: paints samples identification according Table 2 and also additional samples without resin, from left to right and from top to bottom. First line, samples: 11 with only MWP without PVA; 13 with MWP; 2 with RSP; 3 with YSP; 7 with RSP and MWP; 4 with YSP and MWP; 4 with RSP and MWP; 7 with YSP and MWP; 12 with MWP. Second line, samples: 6 with RSP and MWP; 10 with YSP and MWP; 1 with only YSP without PVA; 1 with only RSP without PVA; 6 with YSP and MWP; 9 with RSP and MWP; 11 with MWP; 8 with YSP and MWP; 5 with RSP and MWP. Third line, samples: 10 with RSP and MWP; 1 with YSP; 3 with RSP; 5 with YSP and MWP; 9 with YSP and MWP; 1 with RSP; 2 with YSP; 8 de RSP with MWP.

presented, it was found that the marble waste pigment (MWP) shows particles with granulometry similar to that of a silty material, while the red soil pigment (RSP) is clayey and the yellow soil pigment (YSP) is silty-clayey. Note that the MWP particles have higher particle size than the RSP and YSP particles, but still within the range recommended for the production of paints, according to Oates [53]. X-ray fluorescence (XRF) results are shown in Table 4. It is observed that the waste is mainly composed by compounds based on CaO. Natural and precipitated calcium carbonate, the basic chemical composition of which is CaO, is widely used as mineral filler in the production of paints [7]. While the soils are mainly formed by compounds based on SiO2 e Al2O3. Mineralogical characterization, performed by X-ray diffraction (XRD) can be seen in Fig. 4. Based on the mineralogical analysis it is observed that the MWP has calcite, dolomite, quartz and muscovite. RSP has kaolinite, gibbsite, quartz, goethite and hematite. YSP shows kaolinite, quartz, gibbsite, goethite and hematite. Figs. 5–7 show the morphology of the particles that make up the pigments. The MWP has particles of various sizes and shapes, presenting mainly nodular and rounded vertices, despite the irregular morphology. RSP is mainly composed of small granular particles, prone to agglomeration. YSP is composed of lamellar and granular particles, also with varied shapes and more angular vertices.

3. Results and discussion 3.2. Paint characterization and performance 3.1. Pigment characterization The results of the physical characterization and the pH of the pigments can be seen in Table 3 and the granulometric distribution curve of the pigments is shown in Fig. 3. Based on the results

Table 5 shows the results of paint characterization and performance: solids content (NC), pH, PVC (Pigment Volume Concentration), hiding power (HP) and abrasion resistance (AR). Table 6 shows the adjusted regression equations (p-value < 0.05)

Legend: MWP – Marble waste pigment: RSP – Red soil pigment; YSP – Yellow soil pigment.

Fig. 3. Granulometric distribution curves of marble waste and soil pigments.

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Table 4 Results of pigment FRX analysis. Pigment

CaO

MgO

SiO2

K2O

SO3

Al2O3

Fe2O3

TiO2

Marble waste pigment Red soil pigment Yellow soil pigment

76.59 <1 <1

16.68 – –

4.91 34.48 42.67

1.02 – –

0.77 1.57 1.53

– 43.34 40.69

– 17.96 12.07

– 2.41 2.22

Fig. 5. SEM image of the particle shape of the marble waste pigment highlighting the nodular particles with rounded vertices (Mag. = 5000 X).

Fig. 6. SEM image of the particle shape of the red soil pigment, highlighting the nodular particles with small dimension (Mag. = 5000 X). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

Fig. 4. Result of XRD analysis of the pigments: a) MWP; b) RSP; c) YSP.

corresponding to NC, pH, HP and AR, for each mix planning, with the respective R2 values, representing the adjustment of the model. Note that, according to Table 5, that all the paints manufactured with MWP only (samples 11, 12 and 13) showed hiding power (HP) above the normative specification economy latex paint that is 4.0 m2/L [38]. This result is related to the fact that paints manufactured with MWP have a higher solids content with the optimum viscosity. One of the factors that may have contributed to this effect was the pigment-polymer interactions, considering, for example, that PVA resin can adsorb MWP in the pH range studied and prevent the agglomeration of these pigments [54,55] and dispersion of the particles contributes to the increase in HP [56].

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PVA concentrations and high MWP concentrations, the HP is increased. The best results were obtained with no increase of SP in the southeastern region of the graph. It is noted that the addition of MWP as a mineral filler in SPbased paints contributed to the increase of its HP. According to Karakas and Celik [14], the use of mineral fillers such as calcium carbonate increases the opacity of the paint while it acts as a spacer for the other pigments. Thus, electrostatic interactions between particles of paints produced with MWP may have contributed to HP. Moreover, calcium carbonate, which is the main constituent of marble waste, has a refractive index of 1.58 [28]. Although its refractive index is not very expressive when compared to other mineral fillers, it can be offset with the appropriate PVC (pigment volume concentration) of the system [17]. It should also be noted that the structure of calcium carbonate and the marble itself may contribute to dispersing light. Most of the light that penetrates the surface undergoes multiple internal reflections and diffractions, with good optical dispersion, thus reducing the possibility of light reaching the substrate [59,60,61]. These factors can also help to explain the very high HP value shown by sample 11, in addition to this sample having the highest NC of the formulas studied and good interaction with the resin, facilitating its dispersion. Of the samples produced with SP as sole pigment, only one achieved the minimum value specified for HP: 4 m2/L. This sample was produced with YSP and with the highest PVC content in comparison with the others. A slightly lower HP is also noted for paints made with RSP. RSP has a higher percentage of clay fraction and, more specifically, of iron oxide compared to the other pigments. In this case, in paints with RSP only, the pigment dispersion process becomes more difficult, considering the ion exchange of the clay minerals. The dispersion of the pigments is directly associated with the stability and homogeneity of the paint and, consequently, with hiding power [17]. Moreover, when iron oxide is derived from its natural form, it has low tinting strength and is not opaque [28]. According to Alabi and Omojola [62] the ideal composition for iron oxide in pigments should be below 2%.

Fig. 7. SEM image of the particle shape of the yellow soil pigment, highlighting lamerar particles with more angular vertices (Mag. = 5000 X). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

There is an antagonistic relationship between PVA and MWP, according to the negative term of the equation (ac), referring to HP in Table 6. To increase HP, more MWP should be incorporated into the mixture and PVA reduced as, when the amount of PVA resin in the paint increases, PVC decreases, and the pigments are mainly responsible for the opacity of the film [57,17]. In the case of mixes with YSP, antagonism between SP and MWP influenced HP, probably due to the properties of the YSP and the interaction between particles. Research by Palomino et al. [58] for mixtures with kaolinite and CaCO3 show a similar result. They have shown that particles with sharp edges facilitate flocculation at high solids ratios. And YSP has a lamellar format with sharp edges, which may have contributed to flocculation in systems with higher solids contents. Response surface graphs for HP are presented in Fig. 8. Interactions between all components of the mixtures can be visualized by the level curves shown. In both, it is clear that for low to medium

Table 5 Characteristics and results of performance tests for the paints produced. Sample

1 2 3 4 5 6 7 8 9 10 11 12 13

MWP and/or YSP

MWP and/or RSP

NC (%)

pH

HP (m2/L)

AR (cycles)

PVC

NC (%)

pH

HP (m2/L)

AR (cycles)

PVC

23.76 23.45 22.45 30.72 30.93 36.46 35.86 35.09 45.35 46.61 58.70 55.70 49.17

5.04 4.98 4.78 7.23 7.11 7.39 7.21 7.10 7.32 7.17 7.44 7.17 6.96

4.61 3.22 2.67 4.63 2.80 5.51 3.45 2.91 5.62 4.31 15.63 5.46 4.35

22.05 69.75 219.45 69.45 176.25 45.90 159.75 215.10 100.05 195.90 60.83 100.67 141.67

0.77 0.67 0.56 0.72 0.61 0.77 0.66 0.56 0.71 0.60 0.76 0.65 0.55

21.18 21.00 20.92 24.66 25.44 30.69 30.03 29.70 40.53 36.99 58.70 55.70 49.17

5.40 5.20 5.07 7.34 7.28 7.47 7.30 7.22 7.36 7.19 7.44 7.17 6.96

2.78 2.63 2.32 4.38 3.17 6.72 3.40 2.51 5.23 3.63 15.63 5.46 4.35

23.55 80.10 256.80 59.25 201.15 43.35 167.55 229.05 106.81 215.25 60.83 100.67 141.67

0.76 0.65 0.54 0.71 0.60 0.76 0.65 0.55 0.71 0.60 0.76 0.65 0.55

Table 6 Valid regression equations for paint manufactures. Parameter

MWP and/or YSP Regression equations

NC (%) pH HP (m2/L) AR (ciclos)

yˆ yˆ yˆ yˆ

= = = =

25.93a + 22.67b + 66.99c  20.05bc 4.83a + 5.23b + 8c + 37.93abc 1.24a + 4.90b + 28.42c  58.48ac  18.25bc 826.40a  212.10b + 17.80c – 766.30ac + 1204.90abc

a – PVA resin; b – soil pigment; c – marble waste pigment.

MWP and/or RSP R

2

0.99 0.91 0.87 0.93

Regression equations yˆ yˆ yˆ yˆ

= = = =

20.15a + 21.98b + 68.58c  62.06bc 4.77a + 5.66b + 8.03c + 34.99abc 4.40a + 1.31b + 29.07c  70.03ac 1097.00a 290.00b + 46.00c  1251.00ac + 1513.00abc

R2 0,99 0,90 0,84 0,91

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Fig. 8. Response surface graphs for HP as a function of component ratios, defined between 0 and 1.

The AR value for the ternary mixes was influenced by all its components, but especially by the PVA resin, as shown by the high value of its coefficient (a) in Table 6. The coefficient of the PVA and MWP double interaction (ac) also showed a considerable value, but with a negative sign. The highlight, however, was for the triple interaction coefficient (abc), which suggests a high synergistic effect. This means that the combination of the three components leads to higher AR values compared to the individual components. From the response surfaces of Fig. 9 we can see the RA level curves as a function of the paint composition, obtained from a special cubic model. The 13 experimental points are also represented on the graph. A high synergistic effect can be observed at the top center of the chart. The highest RA values are around point 8 (about 1/3 of each component). High values for abrasion resistance are important as they indicate that the paint will have greater durability. In none of the paints manufactured with the lower limit of resin in solution (20% by mass) and with high values of PVC (above 0.72) was the minimum value of abrasion resistance of 100 cycle met (Table 5). In this case there is not enough binder to coat all the pigment particles, which results in flocculations and the appearance of pores that compromise the integrity of the film [35]. For paints with SP as sole pigment, the AR values were only satisfactory when produced with the upper limit of the resin in solution (40% by mass) and with PVC values in the order of 0.56. In such

mixtures pH values around 5 are observed, which, according to Yamak [63], is the optimum value for PVA performance, considering its reactivity index. The biggest problem in this case is that high resin contents make paint expensive. Paints produced with MWP as the sole pigment achieved satisfactory values of abrasion resistance above the average value of resin percentage (30% by mass), considering the range studied, and for PVC values around 0.65. This result was possible with pH on the order of 7. The most probable hypotheses for this phenomenon are related to particle-binder interactions and the morphology of the pigment particles. Studies by Kelly and Hutchings [64] indicated that wear from friction was lower in materials consisting of round particles of calcite. Moreover, according to Yamak [63] and Li et al. [65], the increase in pH increases the solubility of the resin by exposing hydroxyl groups and promoting interaction with water, thus contributing to the pigment-binder bond. And, the better the pigment packaging by the resin, the better the abrasion resistance. The greatest increases in abrasion resistance occurred through the synergistic effect of the interaction between all components of the mix, namely MWP, SP and PVA. A possible explanation for this may be found in the basis of electrostatic interactions. According to the pH values of the samples produced and studies by Palomino et al. [58], Karakas et al. [66,55] and Karakas and Celik [14,67], there is a strong indication that the surface charge of

Fig. 9. Response surface graphs for AR as a function of component proportions, defined between 0 and 1.

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MWP is positive while that of SP is negative. Also according to zeta potential intensity, MWP may act as a spacer, improving dispersion of particles via interaction with polymer traces. This phenomenon has a positive effect on the good distribution of the particles. Deflocculation of the particles, together with good interfacial adhesion, is directly related to the increased abrasion resistance of the paint [65,68]. However, more studies are needed to reveal possible reasons for this behavior, as paint is a very complex system composed of several ingredients that can directly affect the chemistry of interactions between particles. For example, Palomino et al. [58] states that these interactions are also affected by particle geometry, relative size, solids content, pH and surface fluid effect. 3.3. Ideal formulas The optimal regions of the performance parameters was able to be outlined with the desirability statistical function, based on the normative limits. ABNT NBR 15079:2011 stipulates that HP values must be equal to or greater than 4 m2/L, and for AR, 100 cycles, considering economical paints. According to Table 5, five samples met both normative performance specifications. The percentages of its components were as follows: sample 12 (0.3 PVA and 0.7 MWP) and 13 (0.4 PVA and 0.6 MWP), with MWP as the sole pigment; 9 (0.25 PVA, 0.175 YSP and 0.575 MWP) and 10 (0.35 PVA, 0.175 YSP and 0.475 MWP), of YSP and MWP; and 9 (0.25 PVA, 0.175 RSP and 0.575 MWP), of RSP and MWP. It was found that samples 9 and 10 were produced with the highest proportions of MWP as extender of the range studied. The desirability of the samples is shown on the response surfaces of Fig. 10. In both, it is clear that, for medium concentrations of PVA, low of SP and high of MWP, the desirability of the paints increases, considering the range studied. There is a tendency to increase the desirability for higher MWP levels in the graphs. The indicated formula with the highest total desirability was paint with 30% PVA, 0% SP and 70% MWP, located in the extreme right region of the graph. The ideal formulas underwent microscopic analysis of their films. As well as the samples that met performance requirements (samples 9, 10, 12 and 13), samples 2 (0.3 PVA and 0.7 SP) and 7 (0.3 PVA, 0.35 SP and 0.35 MWP) were characterized for each type of SP. They were chosen because of their high desirability and with the purpose of serving as a parameter for comparison. The thickness and roughness of the films can be seen in Table 7.

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Figs. 11 and 12 show the profiles used for measuring the thickness of each paint film and demonstrate the difference between the part of the cover which was painted and the unpainted part as well as the roughness variation of the samples. Analysis of Table 7 and Figs. 11 and 12 indicates that as MWP was added to the formulas, the paint film became less rough but denser and thicker, also considering the increase in PVA. As the paint was applied manually, slight variations in film thickness are expected. In general, the ideal paint also had the lowest values of roughness. It should be noted that RSP paints, with less rough films than YSP paints, had slightly higher RA values. This reduction of the roughness and improvement of the performance parameters can be explained by interactions between particles and by the adsorption phenomena mentioned above. Something that may also contribute to decreased roughness is the packaging of the particles, which is associated with the shape of the grains. These characteristics can be seen in Figs. 13–15, in which scanning electron microscopy (SEM) images of the films of the ideal formulas are shown. SEM analyses for the YSP paint confirmed the presence of pigments with varied, spherical, nodular and lamellar shapes. These heterogeneities are more expressive in samples with MWP added. The coating of the particles by the resin was very noticeable in sample 10 (Fig. 13c). Superficial inspection of the RSP paint films, using SEM, indicates the relative predominance of small particles. Fig. 14a shows the existence of large agglomerations, as expected. With the addition of MWP, there is a greater dispersion of the particles throughout the film. In the MWP paint films, Fig. 15 shows the predominance of nodular elements, rounded edges, and larger dimensions compared to previous samples. Moreover, the coating and adsorption of MWP particles by the resin is clear, especially in Fig. 15b. 3.4. Evaluation of paint durability The results of microbial analysis for the MWP, YSP and RSP paints are shown in Table 8. The paints were produced with the highest pigment ratio of the range studied. The MWP paint did not show any bacterial growth, however in the dishes containing PDA culture medium the development of a fungal colony was observed. After microscopic observations the fungus was identified as Aspergillus sp. (Fig. 16). In YSP paint, in turn, the occurrence of fungi and bacteria was observed. The fungal isolates present in the YSP paint were the same as those in the MWP paint shown in Fig. 16. On the dishes

Fig. 10. Desirability graphs for MWP and/or YSP and MWP and/or RSP paints, respectively.

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Table 7 Thickness and roughness of the paint samples produced. Paint

Sample

Mean thickness (mm)

Mean roughness (mm)

Mean square root of roughness (mm)

MWP and/or YSP-based paint

2 7 9 10 12 13 2 7 9 10 12 13

48.9 77.0 60.9 95.6 171.1 216.3 31.1 46.7 69.6 82.2 171.1 216.3

7.4 10.2 8.0 9.8 6.1 7.4 5.8 8.8 7.6 9.5 6.1 7.4

10.0 14.1 10.7 12.9 7.9 9.6 8.6 11.4 9.8 12.2 7.9 9.6

MWP and/or RSP-based paint

Fig. 11. Profiles of MWP and/or YSP paints for determining film thickness and evaluating roughness, according to the numberings in each sample.

Fig. 12. Profiles of MWP and/or RSP paints for determining film thickness and evaluating roughness, according to the numberings in each sample.

containing 523 culture medium, bacterial growth was seen (Fig. 17) and the 16S region sequencing results identified this bacterium as being Bacillus sp. According to studies by Opperman and Gull [69] and Grant et al. [70], among the main groups of microorganisms most commonly isolated in water based paints are Bacillus sp. and fungi of the genus Aspergillus. In the RSP paint, there was no manifestation of the presence of fungi or bacteria. One of the factors that may have contributed to this was the low percentage of organic matter in this pigment; the lowest of the pigments analyzed, according to the characterization data. According to Obidi et al. [71], this indicates that there are less nutrients available to encourage microbial growth in the paint. It is worth mentioning that in none of the pigments studied was there a significant occurrence of organic matter

usable for the growth of these heterotrophic organisms. However, the medium can also serve as a nutrient for microbial activity, albeit less pronounced. Thus, it can be assumed that RSP-based paint has not been contaminated by deleterious bacteria or fungi in the manufacturing process or from its raw material. Studies by Obidi et al. [71] also suggest that there is a latency period until exponential growth of deleterious microorganisms is observed. Thus, the microbial presence in the samples indicates that its shelf-life may be adversely affected and that the incorporation of biocides during the production process may be of interest, since this could contribute to increased durability of the paint. The growth of microbial species in the paint requires the presence of moisture in the substrate [72], and fungi do not grow in closed cans, acting only on the paint film, forming a visible surface

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Fig. 13. SEM of the most desirable paints for YSP and YSP with MWP (Mag = 3000 X): a) Sample 2, YSP only; b) Sample 9, with 0.175 YSP and 0.575 MWP by mass; c) Sample 10, with 0.175 YSP and 0.475 MWP by mass.

Fig. 14. SEM of the most desirable paints for RSP and RSP with MWP (Mag = 3000X): a) Sample 2, RSP only; b) Sample 9, with 0.175 RSP and 0.575 MWP by mass; c) Sample 10, with 0.175 RSP and 0.475 MWP by mass.

Fig. 15. SEM of ideal paint final film with MWP (Mag. = 3000 X): a) Sample 12; b) Sample 13.

Table 8 Synthesis of the occurrence and identification of fungi and bacteria present in MWP, YSP and RSP based paints. Paint

Bacteria

Identification

Fungus

AR (cycles)

MWP: sample 11 YSP: sample 1 RSP: sample 1

no yes no

– Bacillus sp. –

yes yes no

Aspergilus sp. Aspergilus sp. –

with a dark coloration. In this case, moisture from the substrate and the environment must be controlled. Thus, to extend the evaluation of the paint durability, the samples were applied on a substrate of their own and subject to natural weathering. The samples suffered rain, wind and solar radiation.

During the sixteen months of exposure, the presence of pathological manifestations and the quality of the paint were examined. At the end of this period the galvanized plates that partially protected the frames were removed and it was also possible to evaluate the difference in color and appearance between the part exposed to

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Fig. 16. Visualization of the macroscopic and microscopic appearance of the Aspergilus sp fungus present in MWP and YSP paint samples: a) Macroscopic image of the plate with BDA culture medium; b) Growth of colonies observed under stereoscopic microscopy (50x); b) Conidiophore containing conidia of Aspergillus sp, observed under optical microscopy.

Fig. 17. Plates containing bacterial growth 523 culture medium in YSP paints.

weathering and the protected part. These results are shown in Table 9. The results were also compared with the meteorological data of the exposure region (Table 10). As can be seen in Table 9, the worst results were from reference samples manufactured without any addition of PVA. Still according to Table 9, of the paints produced with all the components, there were some pathological manifestations only in samples based on RSP, with little or no addition of MWP. There was no mold in any of the paints. Studies developed by Zacarías et al. [73] indicate the inactivation of conidia under visible light, regardless of the paint, even without the use of fungicides. Moreover, an important factor for fungal growth is the high relative humidity in the environment and the lack of ventilation, and there were no such

conditions at the site of exposure of the samples. Thus, despite the results of the microbial analysis, the paints did not show development of fungi that could compromise their durability. Meteorological information for the region in which the paints were exposed, shown in Table 10, indicate that the most critical month for the samples in relation to rainfall is November 2018, while for solar radiation, the most critical period was from January to March 2019. Table 9 indicates that the RSP paints, even with high binder rate, showed cracking and peeling. This is expected, as the high specific surface area of RSP, much larger than the other pigments, increases the demand for the resin and makes the formation of a homogeneous film difficult. And the resin is mainly responsible for the adhesion of the paint film to the substrate. However, it can be seen, in accordance with Fig. 18, which shows the result of some samples after 72 weeks of exposure, that for the same percentage of binder, additions of MWP in the paint formula contribute to increased durability of the paint. The increase in extender volume was expected to cause a decrease in the weatherability of the paint due to increased PVC in the paint composition [73]. However, according to the results shown in Fig. 18 and in Table 9, the increase of MWP lead to greater durability of the samples. This is probably due to the ideal PVC range in the formulas studied and to the result of the electrostatic interactions between

Table 9 Results of test involving exposure to weathering and color difference of the samples quantified by Delta-E. Sample

Color alteration (Delta-E)

MWP and/or YSP paints

Sample

Color alteration (Delta-E)

Pathological manifestations

1 1* 2 3 4 5 6 7 8 9 10 11 11* 12 13

8.02 8.48 7.79 7.44 7.22 7.04 5.98 6.15 6.81 5.74 5.92 2.20 4.13 2.01 1.84

*Samples made without PVA resin.

MWP and/or RSP paints Pathological manifestations

Cracks

Peeling

Mold

No No No No No No No No No No No No No No No

No Yes No No No No No No No No No No Yes No No

No No No No No No No No No No No No No No No

1 1* 2 3 4 5 6 7 8 9 10 11 11* 12 13

6.93 7.09 6.56 5.42 6.57 4.50 4.03 4.58 4.97 4.46 5.68 2.20 4.13 2.01 1.84

Cracks

Peeling

Mold

Yes Yes Yes Yes Yes Yes No No Yes No No No No No No

Yes Yes Yes Yes Yes Yes Yes Yes Yes No No No Yes No No

No No No No No No No No No No No No No No No

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Deise Mara Garcia Alves Tressmann et al. / Construction and Building Materials 241 (2020) 117976 Table 10 Weather information recorded by the Weather Station in the test region. Month

Meteorological information

Radiation (KJ/m2)

Rain (mm)

987.9 1117.9 989.9 1179.0 1102.7 1191.1 1149.3 1691.8 1235.6 1290.6 1126.3 910.3 1000.8 1209.0 1095.7 1128.2 1278.6

3.0 9.0 85.4 56.8 96.0 274.6 97.6 30.4 155.8 130.8 115.4 52.6 24.0 1.0 7.6 60.4 9.0

Temperature (°C)

June 2018* July 2018 August 2018 September 2018 October 2018 November 2018 December 2018 January 2019 February 2019 March 2019 April 2019 May 2019 June 2019 July 2019 August 2018 September 2018 October 2018

Mean

Maximum

Minimum

17.6 16.3 17.4 19.4 21.2 21.0 21.1 23.8 23.0 22.5 21.8 19.9 17.8 15.7 17.3 20.4 21.5

27.5 27.9 28.2 30.6 33.0 30.8 31.4 35.1 35.3 32.9 30.8 29.7 29.8 28.9 30.7 36.1 34.6

8.8 8.2 8.7 9.3 13.1 15.1 12.4 16.5 17.1 15.9 15.1 11.3 8.2 5.2 5.6 10.9 11.9

*After day 12 **Up to day 25. Source: UFV [46] e UFV [47], adapted.

Fig. 18. Red soil pigment-based paints after 72 weeks of exposure with incremental increases in MWP percentage. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

SP and MWP particles. RSP sample 5, shown in Fig. 18, was made with 17.5% MWP by mass, sample 7 with 35% and sample 10 with 47.5%. Besides that, after 72 weeks in the natural weathering exposition there was no biological growth in the samples in both conditions of exposition. Table 9 also indicates that the ideal formulas did not present pathological manifestations during the time of the test, and that these paints, mostly, had the lowest color variation of the samples studied, according to the Delta-E (DE). It is noteworthy that paints made with MWP as a single pigment, without the addition of SP, have an (DE) value below 2 or close to 2, and, according to ColorMine [52], (DE) values below 2 indicate that there is no color difference noticeable. The photolytic stability and water resistance of the paint are probably due to the properties of the pigments and to the formation of a consistent film with a more homogeneous distribution of the particles, pigment coated by the resin and adhesion to the substrate [74]. It should also be considered, according to Buxbaum and Pfaff [75], that inorganic pigments have greater light fastness. Besides that, Galvão et al. [23] studied the resistance to natural weathering of commercial paints using a methodology similar to

that of ASTM G7 [48] and exposing the paints to weather variations similar to those presented in Table 10. Galvão et al. [23] analyzed a latex PVA paint and an acrylic latex paint of economic category. The results obtained for delta E were 11.7 for PVA paint and 3.4 for acrylic paint. Comparing the delta E results of commercial paints and produced paints, it is observed that many paints analyzed in this study performed similarly to the paints available in the Brazilian market. In addition, the response surface graphs for Delta-E (DE) of the samples tested are shown in Fig. 19. Based on their analysis we can conclude that in order to achieve DE values lower than or close to 2 units, SPs must be reduced or cut out and MWP levels increased. Similar results were obtained in studies by Ferreira et al. [76] for vinyl paints with CaCO3, which had DE values below 2 and insignificant color variations. Ferreira et al. [76] and Tao et al. [77] also showed that calcium carbonate associated with TiO2 or Fe2O3 has the ability to absorb UV radiation. A similar effect can occur in paints with SP and high MWP levels, considering the interaction between their components. High UV radiation absorption is associated with protecting pigmentation and polymers from this harmful radiation [75].

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Fig. 19. Three-dimensional surface response graphs for the Delta-E: a) MWP and/or YSP; b) MWP and/or RSP.

4. Conclusion In this study, the possibility of using marble waste as a pigment in the manufacture of PVA latex paints was investigated, both in the situation of active pigment and as mineral filler for soil pigment-based paints. The conclusions of this research are as follows:
All paints manufactured with marble waste pigment (MWP) as active pigment showed hiding power (HP) above the normative specification. This is due to the high solids content (NC) of the formulas and to pigment-polymer interactions, according to the pH of the samples, influenced predominantly by the effective buffering capacity of MWP.
Soil pigment (SP) paints which did not meet the HP regulatory limit were those manufactured without adding MWP or with percentages below 40% MWP. Adding MWP, as a mineral filler, to SP-based paints contributed to increasing the HP. This is because MWP acted as a spacer for the other pigments and also made it possible to manufacture paints with higher NC with ideal viscosity.
In terms of abrasion resistance (AR), in paints with SP only, the normative requirement was met only with 40% PVA resin, the highest percentage of the range studied. For MWP paints, it was possible to achieve the normative values above 30% of PVA. However, the greatest increases in abrasion resistance occurred through the synergistic effect of the interaction between all components of the mix, namely MWP, SP and PVA. In these mixtures, above the percentage of 25% resin AR was satisfactory. This is because interactions between particles enabled the resin to coat the pigments.
Five samples met the performance specifications for both HP and AR. The percentages of the components in these mixes were as follows: 0.3 PVA and 0.7 MWP; and 0.4 PVA and 0.6 MWP, with MWP as the sole pigment; 0.25 PVA, 0.175 YSP and 0.575 MWP; and 0.35 PVA, 0.175 YSP and 0.475 MWP, of YSP (yellow soil pigment) and MWP; and 0.25 PVA, 0.175 RSP and 0.575 MWP, RSP (red soil pigment) and MWP. Paint produced with MWP as sole pigment achieved the satisfactory performance above the average value for the percentage of resin, considering the interval studied. And for SP paints, higher MWP ratios as extender of the range studied provided the best results.


In paints manufactured with the highest percentage of each pigment individually (80% by mass), the presence of the fungus Aspergillus sp. Was detected in the MWP sample. For the YSP paint, the same genus of fungus was observed as well as the bacterium Bacillus sp. No deleterious microorganism appeared in the RSP paints. This is due to the very low percentage of organic matter in the RSP and the absence of contamination during the manufacturing process or from its raw material.
After 72 weeks of exposure to natural weathering, there was no formation of dark mold spots in any of the paints, demonstrating the absence of colonization of filamentous fungi in the material. This was because there were no conditions conducive to its development, such as the presence of moisture in the substrate.
It was also observed that, for the same percentage of binder, MWP added to the paint formula contributed to increased paint durability and greater photolytic stability. This is due to the ideal PVC range in the formulas studied, the properties of MWP and the good distribution of the particles in the paint film, well conditioned by the binder. The results obtained in this study indicate that paints manufactured with marble waste as active pigment can meet the normative specifications for economical latex paint and that the performance of the paints produced with soil pigments was improved with incorporating MWP as mineral filler. Thus, MWP can contribute to the production of low-cost, high-performance building paint and also help the environment, while enabling the appropriate disposal of waste and minimizing the extraction of raw materials.

CRediT authorship contribution statement Deise Mara Garcia Alves Tressmann: Writing - original draft, Data curation, Formal analysis, Investigation, Validation, Writing - review & editing. Leonardo Gonçalves Pedroti: Conceptualization, Methodology, Supervision. Anôr Fiorini de Carvalho: Resources. José Carlos Lopes Ribeiro: Validation. Fernando de Paula Cardoso: Writing - review & editing, Methodology. Márcia Maria Salgado Lopes: Writing - review & editing. André Fernando de Oliveira: Formal analysis. Sukarno Olavo Ferreira: Resources.

Deise Mara Garcia Alves Tressmann et al. / Construction and Building Materials 241 (2020) 117976

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