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Formation of nanostructured TiO2-anatase films on the basalt fiber surface
SCT-20297; No of Pages 10 Surface & Coatings Technology xxx (2015) xxx–xxx
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Formation of nanostructured TiO2-anatase films on the basalt fiber surface Małgorzata Cieślak a, Grzegorz Celichowski b, Patrycja Giesz a,b,⁎, Alicja Nejman a, Dorota Puchowicz a, Jarosław Grobelny b a b
Textile Research Institute, Scientific Department of Unconventional Technologies and Textiles, 5/15 Brzezinska St., 92-103 Lodz, Poland University of Lodz, Faculty of Chemistry, Department of Materials Technology and Chemistry, 163 Pomorska St., 90-236 Lodz, Poland
a r t i c l e
i n f o
Article history: Received 26 December 2014 Revised 14 May 2015 Accepted in revised form 31 May 2015 Available online xxxx Keywords: TiO2 Sol–gel deposition Basalt fibers
a b s t r a c t The direct method of TiO2-anatase coating of basalt fibers and silicon (Si) wafers using the sol–gel dip-coating technique and different subsequent treatments is presented. In order to obtain a structural variety of TiO2 coatings, two kinds of synthesis, with and without the surfactant, were carried out. Hexadecyltrimethylammonium bromide (CTAB) in the concentration of 1%, 3% and 5% was used as a pore-shaping agent. The samples with CTAB were treated in two ways: by calcination at 500 °C and by low-temperature air plasma treatment and calcination, while the samples without CTAB were only treated by calcination. The results of the TGA/DTG and FTIR/ ATR analyses show that the CTAB decomposition rate depends on the content of the surfactant and the time of plasma treatment. The TiO2 anatase form was confirmed by the Raman and XRD analyses of the obtained layers. The nature and the temperature range of the transformation of the amorphous form of TiO2 to anatase were evaluated on the basis of the DSC analysis. The SEM/EDS results show the various structures of TiO2 layers on the fibers and the reference material and the content of Ti equaling approximately 2%. The percentage of the pore surface in TiO2/5% CTAB layers for Si wafer and basalt fiber after plasma treatment and calcination is 41% and 33%, while that only after calcination equals 31% and 28%, respectively. The type of the substrate and the method of surfactant removing have a strong impact on the structure of TiO2 coatings. © 2015 Elsevier B.V. All rights reserved.
1. Introduction Functionalization of textile materials using nanotechnology is a rapidly developing field of research. There are many ways in which the surface properties of textile materials can be changed and improved by appropriate modification. The selection of suitable textile materials, nanomodifiers and methods of their applications allows obtaining textile products with special properties like bioactive, photocatalytic or UV protective characteristics [1–4]. One of the well-known modifiers is titanium dioxide (TiO2). Photocatalytic TiO2 has been particularly intensively studied over the past several years, also in engineering textile materials. There are many potential applications of TiO2 modified textile materials, including self-cleaning fabrics and air/water filter media [5]. The application of nanomodifiers on flexible substrates such as fibers is challenging due to their different structures and properties. Various approaches as regards the preparation and deposition methods, such as hydrothermal treatment [6], liquid phase deposition
⁎ Corresponding author at: Textile Research Institute, Scientific Department of Unconventional Technologies and Textiles, 5/15 Brzezinska St., 92-103 Lodz, Poland E-mail addresses: [email protected] (M. Cieślak), [email protected] (G. Celichowski), [email protected] (P. Giesz), [email protected] (A. Nejman), [email protected] (D. Puchowicz), [email protected] (J. Grobelny).
[7], impregnation [8], vapor deposition [9,10] and the sol–gel technique [11–17] have been reported. The application of TiO2 is most often carried out on conventional synthetic and natural fibers [1,6,13,18–31]. The direct synthesis of anatase TiO2 on such fibers by the sol–gel method and subsequent high temperature treatment is impossible, because of their insufficient thermal resistance. In the literature, there are a few studies concerning the modification of mineral fibers, mainly glass fibers [32–35]. Mineral fibers, including basalt fibers, due to their unique properties, can be used in difficult conditions, requiring high mechanical, chemical and biological resistance [35–40]. Apart from anticorrosive properties, ideal heat insulation, sound absorption and low moisture absorption, basalt fibers are characterized by high thermal resistance ensuring wide application in a variety of thermal conditions. Moreover, they have advantages over glass and asbestos fibers in terms of environmental and safety aspects. Basalt fibers are used for the manufacturing of various products, such as mats, fabrics, strips and ropes, as corrosion-resistant material in the chemical industry, in high temperature-insulation or as external reinforcement for concrete. Equipped with the purifying properties provided by the TiO2 application, such fibers can be used in many structural or filtering systems. A new generation of basalt fibers with high performance has captured the attention in many purposes and may be a suitable material for functional modifications [38,41–44].
http://dx.doi.org/10.1016/j.surfcoat.2015.05.045 0257-8972/© 2015 Elsevier B.V. All rights reserved.
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The aim of this study was to develop a direct method for obtaining nano-TiO2 anatase layers with various structures on the surface of basalt fibers, using the sol–gel technique and different conditions of aftertreatments. 2. Experimental 2.1. Materials Titanium (IV) isopropoxide Ti(OC3H7)4 (TTIP, 98%, Aldrich) as a Ti precursor, isopropanol (99.5%, POCH S.A.) and hydrochloric acid (Chempur) were used for the preparation of TiO2 sol. The ionic surfactant hexadecyltrimethylammonium bromide (CTAB, 98%, Fluka) as a poreforming agent was tested. TiO2 sol was applied to multifilament yarn made of a basalt fiber with a diameter of 15.2 ± 0.5 μm. This yarn is used in technical woven fabric (DBF GmbH, Germany), which is known for its thermal and chemical resistance (from −260 °C to 800 °C) as well as UV stability. Silicon (Si) wafers 100 (Cemat Silicon S.A.) with the thickness of 320–380 μm were used as the reference substrate material. 2.2. TiO2 sol preparation The sol–gel method was used for the modification of basalt fibers and Si wafers. In order to obtain a structural variety of TiO2 coatings, two approaches were tested: a. Synthesis of TiO2 without CTAB surfactant As much as 0.04 g of hydrochloric acid (HCl 2 mol/L) was added dropwise to the solution containing 1.2 g TTIP in 13.2 g of isopropanol. b. Synthesis of TiO2 with CTAB surfactant As much as 1.2 g of TTIP and 0.04 g of hydrochloric acid (HCl 2 mol/L) were added to the solutions containing the surfactant (1, 3, 5 wt.%, respectively) in 13.2 g of isopropanol. Both ways assumed, according to Fig. 1, that the prepared sols were stirred for 30 min before deposition on the fibers' surface and Si wafers.
2.3. TiO2 thin film preparation Basalt fibers and Si wafers were pre-treated in low-temperature air plasma (50 W Zepto 15.26 MHz) for 10 min. TiO2 sol was applied on
the pre-treated substrates by the dip-coating technique using NIMA dip coater (Technology LB, UK) with a constant rate of 25 mm/min. After deposition, all samples were dried at 100 °C for 2 h. TiO2 coatings without CTAB were calcined in a laboratory oven (SNOL, Lithuania) at 500 °C for 2 h with the heating rate of 5 °C min−1 (Fig. 1a). The samples with CTAB were treated in two ways (Fig. 1b): I. One-stage-calcination in order to achieve simultaneous CTAB decomposition and transformation of the TiO2 gel layer from amorphous to the crystalline anatase state, II. Two-stage-air plasma treatment (50 W, 15.26 MHz, for 1, 2, 3, 4 and 5 h) in order to achieve CTAB decomposition and the subsequent calcination for the transformation process.
2.4. Characterization A thermogravimetric analysis (TGA) of CTAB degradation was carried using a TG 209F1 Libra analyzer (Netzsch, Germany) with the heating rate of 10 °C min−1 under the nitrogen flow rate of 20 ml min−1, over the range 30–700 °C. The samples (3.8 ± 2 mg) were tested in a ceramic crucible. The initial (TOnset) and final (TEnd) temperature of degradation, the temperature in peak maximum degradation (TMax Peak) and loss in mass were evaluated. The assessment of the transformation of the amorphous form of TiO2 to anatase was performed using a differential scanning calorimeter DSC 204F1 Phoenix (Netzsch, Germany) with the heating rate of 10 °C/min under the nitrogen flow rate of 25 ml min−1 over the range 20–600 °C. The samples (4 ± 2 mg) were tested in a ceramic crucible. The initial (TOnset) and final (TEnd) temperatures and the temperature in peak maximum (TMax Peak) were evaluated. As the method confirming the TGA analysis, the infrared spectroscopy technique FTIR/ATR was used. FTIR/ATR spectra were recorded with the resolution 4 cm−1 over the range 600–4000 cm−1 using FTIR spectrometer Vertex 70 (Bruker, Germany). In order to evaluate the TiO2 form and its distribution on the modified substrates, Raman spectra and a mapping analysis were performed using Raman Renishaw InVia dispersive spectrometer (Renishaw, UK) with an infrared λ = 785 nm laser excitation. XRD spectra of TiO2 on basalt fibers were collected to identify the anatase crystal phase. The phase composition of examined samples was measured using X-ray diffraction technique on Empyrean diffractometer (PANalytical), working with Cu Ka (1.541874 A) radiation, equipped with the capillary spinner
Fig. 1. Flow charts presenting the TiO2 coating preparation on basalt fibers and Si wafers a) without CTAB and b) with CTAB.
Please cite this article as: M. Cieślak, et al., Surf. Coat. Technol. (2015), http://dx.doi.org/10.1016/j.surfcoat.2015.05.045
M. Cieślak et al. / Surface & Coatings Technology xxx (2015) xxx–xxx Table 1 List (abbreviations) of examined samples.
Table 2 Results of TGA/DTG analysis of fiber samples.
Basalt fibers Raw
Sample TOnset TEnd [°C] [°C]
1 2 3 4 4 0
Calcined
1 2 3 4 4 0
Calcined
CTAB mass loss [%] Plasma Plasma treated [h] untreated 0
Silicon wafers Raw 4 0 4 0
Calcined
1% 3%
CTAB
Plasma treated [h]
Calcined Applied with TiO2 sol
W W0 W1P4K W1K W3P4K W3K W5P4K W5K
5%
Calcined
F1 F3 F5
Plasma pre-treated
1 2 3 4 5 5 0
TMax Peak
[°C]
5% CTAB
Plasma treated [h]
3% CTAB 5% CTAB
Plasma pre-treated
1% CTAB
Calcined
Applied with TiO2 sol
F F0 F1 F1P1 F1P2 F1P3 F1P4 F1P4K F1K F3 F3P1 F3P2 F3P3 F3P4 F3P4K F3K F5 F5P1 F5P2 F5P3 F5P4 F5P5 F5P5K F5K
3
5 0
table. For the measurements 0.7 mm in diameter capillaries was used. Further data processing was done using ICDD PDF 4 database and HighScore Plus software. The surface morphologies of the samples were studied with two scanning electron microscopes (SEM) Nova NanoSEM 450 (FEI, USA) and Vega 3 (Tescan, the Czech Republic). The elemental composition analysis and maps of Ti distribution were performed with X-ray microanalyzer INCA Energy EDS (Oxford Instruments Analytical, Great Britain) connected with SEM Vega 3. The thickness of coatings and the percentage of the pores' surface in TiO2 films were determined on the basis of the SEM image analysis using the program MicroScan v. 1.5 (MicroScan 1999). The legend of the examined samples is presented in Table 1.
3. Results and discussion 3.1. TGA/DTG and DSC analysis The thermal decomposition of CTAB powder (Fig. 2) starts at 226.2 °C (TOnset) with the maximum at 269.7 °C (TMax Peak). TOnset for F3 and F5 samples is comparable with TOnset of CTAB powder (Table 2,
208.1 271.8 242.0 1.79 224.2 278.2 256.4 2.97 223.3 283.9 256.9 6.15
1
2
3
Calcined 4
5 2 h, 500 °C
1.32 0.95 0.30 0 – 0 1.73 1.21 0.79 0 – 0 3.00 1.83 1.22 0.92 0 0
Fig. 2 — DTG curves b, c, d), while for F1 sample it is by 18.1 °C less. TMax Peak for F1 sample is 242.0 °C and it is about 14 °C less than for F3 and F5 samples. The lower thermal decomposition temperatures for F1 sample are the result of a very small content of the surfactant compared to other samples. The CTAB loss in mass increases in the order F1 b F3 b F5 (Table 2, Fig. 2 — TGA curves b, c, d), which corresponds to the CTAB content in the samples. After 4 h plasma treatment, no additional loss was found in mass for F1 and F3 samples, which suggests complete decomposition of CTAB. For F5 sample, such effect was observed after 5-h plasma treatment (Table 2, Fig. 2 — TGA curve a). It was found that after 1-h plasma treatment in F5 sample 51% of the initial CTAB content was decomposed, while for F3 and F1 the values reached 41% and 26%, respectively (Table 2, Fig. 3). TGA curves for F1P4, F3P4, F5P5 and F are comparable to these obtained for F5K. The calcination process resulted in a complete CTAB decomposition for all tested samples (Table 2, Fig. 2, curves a). DSC analysis shows the transition of the amorphous TiO2 form to anatase (Fig. 4, curve a). The initial temperature of exothermic process starts near 435 °C and ends at 472 °C with the maximum at 451 °C. No changes were observed for raw fibers (Fig. 4, curve b). 3.2. FTIR/ATR analysis On the FTIR/ATR spectrum of CTAB powder (Fig. 5a), two intense bands at 2849 and 2916 cm−1 (C–H stretching vibrations, symmetric and asymmetric), the band at 1478 cm− 1 (CH2 bending vibrations), the band at 909 cm− 1 (C–N stretching) and the band at 723 cm− 1 (CH2 rocking vibrations) are present [45,46]. The results of the FTIR/ ATR analysis confirm the presence of CTAB in F1, F3 and F5 samples (Fig. 5b, c, d — bands at 2916 cm−1, 2848 cm−1 and 1477 cm−1). The intensity of CTAB bands is weaker for the sample with the lower surfactant content. The calcination process resulted in decomposition of the
Fig. 2. TGA/DTG analysis of TiO2 modified basalt fibers with a) 5% CTAB after calcination (F5K), b) 1% CTAB (F1), c) 3% CTAB (F3) and d) 5% CTAB (F5) and CTAB powder.
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Fig. 3. The decomposition rate of CTAB for basalt fibers with 1% CTAB (F1), 3% CTAB (F3) and 5% CTAB (F5) versus time of the plasma treatment.
surfactant, as confirmed by the absence of CTAB characteristic bands for F1K sample (Fig. 5, F1K sample). The results of the FTIR analysis for F3 and F5 samples after calcination are comparable to F1K sample (not shown). After plasma treatment, the intensity of CTAB bands at 2916 cm−1, 2849 cm− 1 and 1478 cm−1 becomes weaker (Fig. 5b, c, d). The ratio of the band at 2916 cm−1 for the sample with 5% CTAB to the sample with 3% and 1% CTAB is 2 and 4, respectively. For the sample with 5% CTAB, the ratio of this band before and after 1, 2, 3, and 4 h of plasma treatment equals 3, 4, 9, and 18, respectively. In F5P5, the surfactant was completely decomposed and the characteristic bands of CTAB in the spectrum were not observed (Fig. 5b). The ratio of the band at 2916 cm−1 for the sample with 3% CTAB after 1, 2, and 3 h equals 3, 5, and 9, respectively. In F3P3, CTAB was still present (weak bands at 2916 cm−1 and 2848 cm−1), but after one more hour of plasma treatment (F3P4), it was also completely decomposed (Fig. 5c). For the sample with 1% CTAB, the intensity of the plasma-treated samples bands is very weak (Fig. 5d). After 2 and 3 h of plasma treatment, CTAB characteristic bands in the spectrum of F1P2 and F1P3 were not observed, but the TGA analysis confirmed the CTAB presence. 3.3. Raman analysis The Raman spectrum of F1 sample (Fig. 6d) shows characteristic bands of CTAB at 127 cm−1, 453 cm−1, and 765 cm−1 corresponding to C–N stretching vibration, weak bands at 1066 cm− 1 and
1131 cm− 1 assigned to C–C stretching vibrations, a strong band at 1307 cm−1 for CH2 torsion vibration, bands at 1447 cm− 1 and 1473 cm−1 assigned to CH2 bending vibrations, bands at 2856 cm− 1 and 2890 cm−1 for CH2 stretching vibrations and a very weak band at 2955 cm− 1 corresponding to N–CH2 and CH3 stretching vibrations [46]. The air plasma treatment resulted in the CTAB decomposition (Fig. 6c) without the alteration of the TiO2 form, and strong bands at 450 cm−1 and 607 cm− 1 are assigned to the amorphous TiO2 form [47]. The peak at 142 cm−1 assigned to TiO2-anatase (O–Ti–O bending vibration) for F1P4K sample indicates the transformation of the amorphous form to anatase, as a result of the calcination process (Fig. 6b). Other anatase bands at 194 cm− 1, 393 cm− 1, 515 cm− 1 and 637 cm−1 [48] were not observed, because there are strong bands of basalt fibers in this range. The spectrum of F1P4K cross-section (Fig. 7c-II) shows that fibers have been modified only on the surface (the band at 142 cm−1). The spectrum in the middle of the cross-section is characteristic for raw basalt fibers (Fig. 7c-I). The spectrum of the F1P4K surface corresponds to basalt fibers and TiO2-anatase. TiO2 coatings are very thin and bands attributed to anatase are obscured by bands of the fibers. At each tested point of the fibers surface the TiO2-anatase form is observed (Fig. 7a, b — white points). The results of the Raman analysis for F3P4K and F5P5K are analogous to the ones described above for F1P4K sample (not shown). 3.4. XRD analysis XRD results for the thin TiO2 coating on the basalt fibers (Fig. 8a) confirm the formation of anatase structure after calcination at 500 °C. XRD spectrum shows the most intense reflection at (2θ) 25.31° corresponding to the (101) plane diffraction peak of anatase. Two less intense reflections at 2θ of 37.76°, 48.05° correspond to the (004) and (200) planes. Other anatase characteristic (211) and (204) planes at 2θ of 55.07° and 62.94° are not visible on XRD spectrum [19]. For raw basalt fibers any reflection characteristics for anatase were observed (Fig. 8b). 3.5. SEM/EDS analysis
Fig. 4. DSC analysis of a) basalt fibers with TiO2 coating before calcination and b) raw basalt fibers (F).
The SEM results of basalt fibers and Si wafers after surfactant decomposition are presented in Figs. 9 and 10. The substantial changes in the
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Fig. 5. FTIR/ATR spectra of a) CTAB powder, TiO2 modified basalt fibers with 1% CTAB (F1), TiO2 modified basalt fibers with 1% CTAB after calcination (F1K); TiO2 modified basalt fibers with b) 5% CTAB (F5) and F5 plasma treated for 1 h (F5P1), 2 h (F5P2), 3 h (F5P3), 4 h (F5P4), 5 h (F5P5); c) 3% CTAB (F3) and F3 plasma treated for 1 h (F3P1), 2 h (F3P2), 3 h (F3P3) 4 h (F3P4); d) 1% CTAB (F1) and F1 plasma treated for 1 h (F1P1), 2 h (F1P2), 3 h (F1P3), 4 h (F1P4).
surface topography are visible for the samples modified with CTAB. During CTAB removing, the porous structure of the TiO2 layer is formed, which depends on the amount of the surfactant.
Fig. 6. Raman spectra of a) raw basalt fibers (F), TiO2 modified basalt fibers with b) 1% CTAB plasma treated for 4 h and calcined (F1P4K), c) 1% CTAB plasma treated for 4 h (F1P4), d) 1% CTAB (F1) and e) CTAB powder.
Similar results were observed also by other scientists [11,49–51]. The higher content of the surfactant results in the formation of larger pores (and also a greater surface area of the pores) in the coatings. The TiO 2 coating on a Si wafer containing 5% CTAB has about five times larger surface area of the pores compared to the samples with 1% CTAB (Fig. 10c, d, g, h). The differentiation of the coating depending on the amounts of the added surfactant is also observed on the fibers (Fig. 9). The texture of the fiber coating has a different nature than that on the Si wafer (size, distribution and shape of the pores). This may be a result of the physico-chemical properties (chemical composition, roughness) and the shape of both types of substrate samples (Figs. 9 and 10). It has also been noted that the way of surfactant removing influences the morphology and texture of the obtained coatings, both in the case of fibers and wafers. The pore diameter of TiO 2/CTAB coatings measured for Si wafers only after the plasma treatment (not shown on SEM images) is bigger (37 ± 7 nm, 62 ± 8 nm and 113 ± 30 nm for 1%, 3% and 5% CTAB, respectively) compared to the results obtained for the same samples after the completion of the two-stage process (33 ± 7 nm, 56 ± 13 nm and 92 ± 29 nm, respectively) (Fig. 9c, e, g), and for the samples after the one-stage process (28 ± 5 nm, 37 ± 9 nm and 58 ± 22 nm, respectively) (Fig. 9d, f, h). The differentiation of the TiO 2 coating on fibers is the lowest for the sample with 1% CTAB (Fig. 10). The coating after the one-stage process (Fig. 10d) is
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Fig. 7. Raman point maps made for a) cross-section and b) surface of TiO2 modified fibers with 1% CTAB plasma-treated for 4 h and calcined (F1P4K) (white points — TiO2 anatase and black points — basalt fiber/lack of TiO2 and c) Raman spectra of F1P4K in the middle of fiber cross-section (I) and on fiber surface (II).
comparable to that after the two-stage process (Fig. 10c). On the basis of the F5K SEM image (Fig. 10h, j), the greatest effect of the surfactant addition is visible for the sample with 5% CTAB. However, the percentage of pores is larger for sample F5P5K, after the two-stage process (Fig. 10g, i). For 3% CTAB, larger structural changes of the coating were also observed for the two-stage process. It was found that calcination of the plasma-treated and untreated coatings resulted in a reduction and distortion of the pores. It may be caused by contractions (movements) of the coatings in the calcination process or
the gaseous products of the surfactant decomposition may change the structure of the coatings. The biggest surface area of the pores was found for TiO 2/5% CTAB coatings after the two-stage process (plasma treatment/calcination): 41% for Si wafer (W5P5K, Fig. 9g) and 33% for fiber (F5P5K, Fig. 10i). TiO2/5% CTAB coatings after the one-stage process (calcination) have a smaller surface area of the pores, namely 31% for Si wafers (W5K, Fig. 9h) and 28% for fibers (F5K, Fig. 10j). As mentioned above, the structures of the coatings on the fibers obtained with the same method differ significantly
Fig. 8. XRD spectra of a) 80 nm TiO2 coating on basalt fibers (F0) and b) raw basalt fibers (F).
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Fig. 9. SEM images of raw Si wafer (a), TiO2 coating (magnification 35,000× and 120,000×) without CTAB (b) and with CTAB on Si wafers (c–h). The percentage of the pore surface (A) and the distribution of the pore diameter (d).
compared to the coatings on the Si wafers. The thickness of these two layers differs also considerably and amounts to 20 nm for wafers and 80 nm for fibers. The results of the SEM/EDS analysis are presented in Fig. 11 and in Table 3. Raw basalt fibers contain traces of Ti 0.3 ± 0.1%, while for all TiO2 -modified samples, the Ti content is 2 ± 0.6%. The SEM/EDS results also show the presence of other elements,
which are components of raw basalt fibers. The content values of individual elements are similar, while a significant increase in the amount of carbon is noticeable for fibers with the TiO2 film (smooth and porous). This is probably related to the removal of residue isopropanol (present in the sol) and/or surfactant (for porous samples) the from TiO2 coating during annealing. The X-ray energy
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Fig. 10. SEM images of raw basalt fibers (a), TiO2 coating (magnification 35,000× and 120,000×) without CTAB (b) and with CTAB on basalt fiber surface (c–h). The percentage of the pore surface (A) for F5P5K (i) and F5K (j) fibers.
spectra for F1K or F1P4K collected from five points do not differ and Ti is evenly distributed on the tested fiber surface. This is confirmed by the maps of the Ti distribution (Fig. 11). 4. Conclusions The nano-layers of TiO 2 -anatase with various structures and thicknesses on the surfaces of basalt fibers (80 nm) and Si wafers (20 nm) using the sol–gel technique and different subsequent treatments were obtained. TiO2 sol samples without and with CTAB surfactant (1%, 3% and 5%) were tested. Two methods of surfactant removing were used: calcination only and low-temperature air plasma treatment with subsequent calcination. From the results of TGA and FTIR/ATR, it was found that CTAB is removed both in the plasma treatment process and during calcination. The decomposition rate of CTAB depends on the content of the surfactant and the time of plasma treatment. The TiO2 coatings obtained by the presented methods are evenly distributed on the fibers surface. The Raman results show that after calcination at 500 °C, TiO2 in the photocatalytically active form-anatase was obtained. The XRD analysis also confirmed the
presence of TiO2 anatase in the coating of basalt fibers, although the intensity of the band characteristic of anatase is low due to the very thin coating. The most intense reflection at (2θ) 25.31° corresponds to the (101) plane diffraction peak of anatase. The DSC analysis showed the transformation of amorphous TiO2 on the fibers to the anatase form in the range 435–472 °C and the exothermic nature of this process. The high thermal resistance of basalt fibers made it possible to carry out the calcination process directly on the fibers' surface. The results of the SEM analysis indicate changes in the surface topography of the samples with the surfactant addition. The plasma treatment before calcination resulted in a greater development of the TiO2 layer structure. The structure of TiO2 layers depends also on the type of the substrate. In the case of Si wafers, the pores have a shape close to circular and their diameter/surface area increases alongside an increase of the surfactant addition. For fibers, the formation of smaller, irregular, channel pores was observed. The greatest diversity of the TiO 2 coating structure was found for the 5% addition of CTAB. In further research, the obtained TiO2 coatings on basalt fabrics with various surface developments will be used in the photocatalysis process.
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Fig. 11. SEM/EDS analysis of TiO2 modified fibers with 1% CTAB a) calcined (F1K), b) 4 h plasma treated for 4 h and calcined (F1P4K) with maps of the Ti distribution on the fiber surface (white spots — Ti).
Table 3 Results of SEM/EDS analysis of raw basalt fibers (F), TiO2 modified fibers (F0), TiO2 modified fibers with 1% CTAB: 4 h plasma-treated and calcined (F1P4K); calcined (F1K). Sample
F F0 F1P4K F1K a b
Elemental content [weight %] C
O
Na
Mg
Al
Si
K
Ca
Ti
Fe
15.1a ± 0.8b 22.5 ± 3.7 24.26 ± 3.7 20.1 ± 3.3
49.7 ± 0.4 43.7 ± 3.5 43.7 ± 1.7 43.8 ± 3.3
2.7 ± 0.1 3.0 ± 0.4 2.0 ± 0.2 1.9 ± 0.8
2.5 ± 0.1 2.2 ± 0.2 1.3 ± 0.2 1.6 ± 0.3
5.9 ± 0.1 4.9 ± 0.2 5.1 ± 0.4 5.8 ± 0.6
16.7 ± 0.5 14.6 ± 0.4 15.2 ± 1.1 17.1 ± 1.6
0.6 ± 0.1 0.5 ± 0.1 0.8 ± 02 0.8 ± 0.2
3.2 ± 0.2 3.1 ± 0.3 2.9 ± 0.5 3.4 ± 0.4
0.3 ± 0.1 2.0 ± 0.5 2.3 ± 0.3 1.9 ± 0.3
3.2 ± 0.2 3.4 ± 0.5 2.5 ± 0.7 3.7 ± 0.5
The averaged values from five measurements. Standard deviation.
Acknowledgments The study was carried out within the Key Project — POIG.01.03.01-00004/08 Functional Nano- and Micro-textile Materials — NANOMITEX cofinanced by the European Union with the financial resources of the European Regional Development Fund and the National Centre for Research and Development within the framework of the Innovative Economy Operational Programme, 2007–2013, Priority 1. Research and development of modern technologies, Activity 1.3. Supporting R&D projects for enterprises undertaken by science establishments, Subactivity 1.3.1. Development projects. The authors would like to thank Mr Damian Batory from Institute of Materials Science and Engineering, Lodz University of Technology for the performance of the XRD analysis.
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Formation of nanostructured TiO2-anatase films on the basalt fiber surface Małgorzata Cieślak a, Grzegorz Celichowski b, Patrycja Giesz a,b,⁎, Alicja Nejman a, Dorota Puchowicz a, Jarosław Grobelny b a b
Textile Research Institute, Scientific Department of Unconventional Technologies and Textiles, 5/15 Brzezinska St., 92-103 Lodz, Poland University of Lodz, Faculty of Chemistry, Department of Materials Technology and Chemistry, 163 Pomorska St., 90-236 Lodz, Poland
a r t i c l e
i n f o
Article history: Received 26 December 2014 Revised 14 May 2015 Accepted in revised form 31 May 2015 Available online xxxx Keywords: TiO2 Sol–gel deposition Basalt fibers
a b s t r a c t The direct method of TiO2-anatase coating of basalt fibers and silicon (Si) wafers using the sol–gel dip-coating technique and different subsequent treatments is presented. In order to obtain a structural variety of TiO2 coatings, two kinds of synthesis, with and without the surfactant, were carried out. Hexadecyltrimethylammonium bromide (CTAB) in the concentration of 1%, 3% and 5% was used as a pore-shaping agent. The samples with CTAB were treated in two ways: by calcination at 500 °C and by low-temperature air plasma treatment and calcination, while the samples without CTAB were only treated by calcination. The results of the TGA/DTG and FTIR/ ATR analyses show that the CTAB decomposition rate depends on the content of the surfactant and the time of plasma treatment. The TiO2 anatase form was confirmed by the Raman and XRD analyses of the obtained layers. The nature and the temperature range of the transformation of the amorphous form of TiO2 to anatase were evaluated on the basis of the DSC analysis. The SEM/EDS results show the various structures of TiO2 layers on the fibers and the reference material and the content of Ti equaling approximately 2%. The percentage of the pore surface in TiO2/5% CTAB layers for Si wafer and basalt fiber after plasma treatment and calcination is 41% and 33%, while that only after calcination equals 31% and 28%, respectively. The type of the substrate and the method of surfactant removing have a strong impact on the structure of TiO2 coatings. © 2015 Elsevier B.V. All rights reserved.
1. Introduction Functionalization of textile materials using nanotechnology is a rapidly developing field of research. There are many ways in which the surface properties of textile materials can be changed and improved by appropriate modification. The selection of suitable textile materials, nanomodifiers and methods of their applications allows obtaining textile products with special properties like bioactive, photocatalytic or UV protective characteristics [1–4]. One of the well-known modifiers is titanium dioxide (TiO2). Photocatalytic TiO2 has been particularly intensively studied over the past several years, also in engineering textile materials. There are many potential applications of TiO2 modified textile materials, including self-cleaning fabrics and air/water filter media [5]. The application of nanomodifiers on flexible substrates such as fibers is challenging due to their different structures and properties. Various approaches as regards the preparation and deposition methods, such as hydrothermal treatment [6], liquid phase deposition
⁎ Corresponding author at: Textile Research Institute, Scientific Department of Unconventional Technologies and Textiles, 5/15 Brzezinska St., 92-103 Lodz, Poland E-mail addresses: [email protected] (M. Cieślak), [email protected] (G. Celichowski), [email protected] (P. Giesz), [email protected] (A. Nejman), [email protected] (D. Puchowicz), [email protected] (J. Grobelny).
[7], impregnation [8], vapor deposition [9,10] and the sol–gel technique [11–17] have been reported. The application of TiO2 is most often carried out on conventional synthetic and natural fibers [1,6,13,18–31]. The direct synthesis of anatase TiO2 on such fibers by the sol–gel method and subsequent high temperature treatment is impossible, because of their insufficient thermal resistance. In the literature, there are a few studies concerning the modification of mineral fibers, mainly glass fibers [32–35]. Mineral fibers, including basalt fibers, due to their unique properties, can be used in difficult conditions, requiring high mechanical, chemical and biological resistance [35–40]. Apart from anticorrosive properties, ideal heat insulation, sound absorption and low moisture absorption, basalt fibers are characterized by high thermal resistance ensuring wide application in a variety of thermal conditions. Moreover, they have advantages over glass and asbestos fibers in terms of environmental and safety aspects. Basalt fibers are used for the manufacturing of various products, such as mats, fabrics, strips and ropes, as corrosion-resistant material in the chemical industry, in high temperature-insulation or as external reinforcement for concrete. Equipped with the purifying properties provided by the TiO2 application, such fibers can be used in many structural or filtering systems. A new generation of basalt fibers with high performance has captured the attention in many purposes and may be a suitable material for functional modifications [38,41–44].
http://dx.doi.org/10.1016/j.surfcoat.2015.05.045 0257-8972/© 2015 Elsevier B.V. All rights reserved.
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M. Cieślak et al. / Surface & Coatings Technology xxx (2015) xxx–xxx
The aim of this study was to develop a direct method for obtaining nano-TiO2 anatase layers with various structures on the surface of basalt fibers, using the sol–gel technique and different conditions of aftertreatments. 2. Experimental 2.1. Materials Titanium (IV) isopropoxide Ti(OC3H7)4 (TTIP, 98%, Aldrich) as a Ti precursor, isopropanol (99.5%, POCH S.A.) and hydrochloric acid (Chempur) were used for the preparation of TiO2 sol. The ionic surfactant hexadecyltrimethylammonium bromide (CTAB, 98%, Fluka) as a poreforming agent was tested. TiO2 sol was applied to multifilament yarn made of a basalt fiber with a diameter of 15.2 ± 0.5 μm. This yarn is used in technical woven fabric (DBF GmbH, Germany), which is known for its thermal and chemical resistance (from −260 °C to 800 °C) as well as UV stability. Silicon (Si) wafers 100 (Cemat Silicon S.A.) with the thickness of 320–380 μm were used as the reference substrate material. 2.2. TiO2 sol preparation The sol–gel method was used for the modification of basalt fibers and Si wafers. In order to obtain a structural variety of TiO2 coatings, two approaches were tested: a. Synthesis of TiO2 without CTAB surfactant As much as 0.04 g of hydrochloric acid (HCl 2 mol/L) was added dropwise to the solution containing 1.2 g TTIP in 13.2 g of isopropanol. b. Synthesis of TiO2 with CTAB surfactant As much as 1.2 g of TTIP and 0.04 g of hydrochloric acid (HCl 2 mol/L) were added to the solutions containing the surfactant (1, 3, 5 wt.%, respectively) in 13.2 g of isopropanol. Both ways assumed, according to Fig. 1, that the prepared sols were stirred for 30 min before deposition on the fibers' surface and Si wafers.
2.3. TiO2 thin film preparation Basalt fibers and Si wafers were pre-treated in low-temperature air plasma (50 W Zepto 15.26 MHz) for 10 min. TiO2 sol was applied on
the pre-treated substrates by the dip-coating technique using NIMA dip coater (Technology LB, UK) with a constant rate of 25 mm/min. After deposition, all samples were dried at 100 °C for 2 h. TiO2 coatings without CTAB were calcined in a laboratory oven (SNOL, Lithuania) at 500 °C for 2 h with the heating rate of 5 °C min−1 (Fig. 1a). The samples with CTAB were treated in two ways (Fig. 1b): I. One-stage-calcination in order to achieve simultaneous CTAB decomposition and transformation of the TiO2 gel layer from amorphous to the crystalline anatase state, II. Two-stage-air plasma treatment (50 W, 15.26 MHz, for 1, 2, 3, 4 and 5 h) in order to achieve CTAB decomposition and the subsequent calcination for the transformation process.
2.4. Characterization A thermogravimetric analysis (TGA) of CTAB degradation was carried using a TG 209F1 Libra analyzer (Netzsch, Germany) with the heating rate of 10 °C min−1 under the nitrogen flow rate of 20 ml min−1, over the range 30–700 °C. The samples (3.8 ± 2 mg) were tested in a ceramic crucible. The initial (TOnset) and final (TEnd) temperature of degradation, the temperature in peak maximum degradation (TMax Peak) and loss in mass were evaluated. The assessment of the transformation of the amorphous form of TiO2 to anatase was performed using a differential scanning calorimeter DSC 204F1 Phoenix (Netzsch, Germany) with the heating rate of 10 °C/min under the nitrogen flow rate of 25 ml min−1 over the range 20–600 °C. The samples (4 ± 2 mg) were tested in a ceramic crucible. The initial (TOnset) and final (TEnd) temperatures and the temperature in peak maximum (TMax Peak) were evaluated. As the method confirming the TGA analysis, the infrared spectroscopy technique FTIR/ATR was used. FTIR/ATR spectra were recorded with the resolution 4 cm−1 over the range 600–4000 cm−1 using FTIR spectrometer Vertex 70 (Bruker, Germany). In order to evaluate the TiO2 form and its distribution on the modified substrates, Raman spectra and a mapping analysis were performed using Raman Renishaw InVia dispersive spectrometer (Renishaw, UK) with an infrared λ = 785 nm laser excitation. XRD spectra of TiO2 on basalt fibers were collected to identify the anatase crystal phase. The phase composition of examined samples was measured using X-ray diffraction technique on Empyrean diffractometer (PANalytical), working with Cu Ka (1.541874 A) radiation, equipped with the capillary spinner
Fig. 1. Flow charts presenting the TiO2 coating preparation on basalt fibers and Si wafers a) without CTAB and b) with CTAB.
Please cite this article as: M. Cieślak, et al., Surf. Coat. Technol. (2015), http://dx.doi.org/10.1016/j.surfcoat.2015.05.045
M. Cieślak et al. / Surface & Coatings Technology xxx (2015) xxx–xxx Table 1 List (abbreviations) of examined samples.
Table 2 Results of TGA/DTG analysis of fiber samples.
Basalt fibers Raw
Sample TOnset TEnd [°C] [°C]
1 2 3 4 4 0
Calcined
1 2 3 4 4 0
Calcined
CTAB mass loss [%] Plasma Plasma treated [h] untreated 0
Silicon wafers Raw 4 0 4 0
Calcined
1% 3%
CTAB
Plasma treated [h]
Calcined Applied with TiO2 sol
W W0 W1P4K W1K W3P4K W3K W5P4K W5K
5%
Calcined
F1 F3 F5
Plasma pre-treated
1 2 3 4 5 5 0
TMax Peak
[°C]
5% CTAB
Plasma treated [h]
3% CTAB 5% CTAB
Plasma pre-treated
1% CTAB
Calcined
Applied with TiO2 sol
F F0 F1 F1P1 F1P2 F1P3 F1P4 F1P4K F1K F3 F3P1 F3P2 F3P3 F3P4 F3P4K F3K F5 F5P1 F5P2 F5P3 F5P4 F5P5 F5P5K F5K
3
5 0
table. For the measurements 0.7 mm in diameter capillaries was used. Further data processing was done using ICDD PDF 4 database and HighScore Plus software. The surface morphologies of the samples were studied with two scanning electron microscopes (SEM) Nova NanoSEM 450 (FEI, USA) and Vega 3 (Tescan, the Czech Republic). The elemental composition analysis and maps of Ti distribution were performed with X-ray microanalyzer INCA Energy EDS (Oxford Instruments Analytical, Great Britain) connected with SEM Vega 3. The thickness of coatings and the percentage of the pores' surface in TiO2 films were determined on the basis of the SEM image analysis using the program MicroScan v. 1.5 (MicroScan 1999). The legend of the examined samples is presented in Table 1.
3. Results and discussion 3.1. TGA/DTG and DSC analysis The thermal decomposition of CTAB powder (Fig. 2) starts at 226.2 °C (TOnset) with the maximum at 269.7 °C (TMax Peak). TOnset for F3 and F5 samples is comparable with TOnset of CTAB powder (Table 2,
208.1 271.8 242.0 1.79 224.2 278.2 256.4 2.97 223.3 283.9 256.9 6.15
1
2
3
Calcined 4
5 2 h, 500 °C
1.32 0.95 0.30 0 – 0 1.73 1.21 0.79 0 – 0 3.00 1.83 1.22 0.92 0 0
Fig. 2 — DTG curves b, c, d), while for F1 sample it is by 18.1 °C less. TMax Peak for F1 sample is 242.0 °C and it is about 14 °C less than for F3 and F5 samples. The lower thermal decomposition temperatures for F1 sample are the result of a very small content of the surfactant compared to other samples. The CTAB loss in mass increases in the order F1 b F3 b F5 (Table 2, Fig. 2 — TGA curves b, c, d), which corresponds to the CTAB content in the samples. After 4 h plasma treatment, no additional loss was found in mass for F1 and F3 samples, which suggests complete decomposition of CTAB. For F5 sample, such effect was observed after 5-h plasma treatment (Table 2, Fig. 2 — TGA curve a). It was found that after 1-h plasma treatment in F5 sample 51% of the initial CTAB content was decomposed, while for F3 and F1 the values reached 41% and 26%, respectively (Table 2, Fig. 3). TGA curves for F1P4, F3P4, F5P5 and F are comparable to these obtained for F5K. The calcination process resulted in a complete CTAB decomposition for all tested samples (Table 2, Fig. 2, curves a). DSC analysis shows the transition of the amorphous TiO2 form to anatase (Fig. 4, curve a). The initial temperature of exothermic process starts near 435 °C and ends at 472 °C with the maximum at 451 °C. No changes were observed for raw fibers (Fig. 4, curve b). 3.2. FTIR/ATR analysis On the FTIR/ATR spectrum of CTAB powder (Fig. 5a), two intense bands at 2849 and 2916 cm−1 (C–H stretching vibrations, symmetric and asymmetric), the band at 1478 cm− 1 (CH2 bending vibrations), the band at 909 cm− 1 (C–N stretching) and the band at 723 cm− 1 (CH2 rocking vibrations) are present [45,46]. The results of the FTIR/ ATR analysis confirm the presence of CTAB in F1, F3 and F5 samples (Fig. 5b, c, d — bands at 2916 cm−1, 2848 cm−1 and 1477 cm−1). The intensity of CTAB bands is weaker for the sample with the lower surfactant content. The calcination process resulted in decomposition of the
Fig. 2. TGA/DTG analysis of TiO2 modified basalt fibers with a) 5% CTAB after calcination (F5K), b) 1% CTAB (F1), c) 3% CTAB (F3) and d) 5% CTAB (F5) and CTAB powder.
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Fig. 3. The decomposition rate of CTAB for basalt fibers with 1% CTAB (F1), 3% CTAB (F3) and 5% CTAB (F5) versus time of the plasma treatment.
surfactant, as confirmed by the absence of CTAB characteristic bands for F1K sample (Fig. 5, F1K sample). The results of the FTIR analysis for F3 and F5 samples after calcination are comparable to F1K sample (not shown). After plasma treatment, the intensity of CTAB bands at 2916 cm−1, 2849 cm− 1 and 1478 cm−1 becomes weaker (Fig. 5b, c, d). The ratio of the band at 2916 cm−1 for the sample with 5% CTAB to the sample with 3% and 1% CTAB is 2 and 4, respectively. For the sample with 5% CTAB, the ratio of this band before and after 1, 2, 3, and 4 h of plasma treatment equals 3, 4, 9, and 18, respectively. In F5P5, the surfactant was completely decomposed and the characteristic bands of CTAB in the spectrum were not observed (Fig. 5b). The ratio of the band at 2916 cm−1 for the sample with 3% CTAB after 1, 2, and 3 h equals 3, 5, and 9, respectively. In F3P3, CTAB was still present (weak bands at 2916 cm−1 and 2848 cm−1), but after one more hour of plasma treatment (F3P4), it was also completely decomposed (Fig. 5c). For the sample with 1% CTAB, the intensity of the plasma-treated samples bands is very weak (Fig. 5d). After 2 and 3 h of plasma treatment, CTAB characteristic bands in the spectrum of F1P2 and F1P3 were not observed, but the TGA analysis confirmed the CTAB presence. 3.3. Raman analysis The Raman spectrum of F1 sample (Fig. 6d) shows characteristic bands of CTAB at 127 cm−1, 453 cm−1, and 765 cm−1 corresponding to C–N stretching vibration, weak bands at 1066 cm− 1 and
1131 cm− 1 assigned to C–C stretching vibrations, a strong band at 1307 cm−1 for CH2 torsion vibration, bands at 1447 cm− 1 and 1473 cm−1 assigned to CH2 bending vibrations, bands at 2856 cm− 1 and 2890 cm−1 for CH2 stretching vibrations and a very weak band at 2955 cm− 1 corresponding to N–CH2 and CH3 stretching vibrations [46]. The air plasma treatment resulted in the CTAB decomposition (Fig. 6c) without the alteration of the TiO2 form, and strong bands at 450 cm−1 and 607 cm− 1 are assigned to the amorphous TiO2 form [47]. The peak at 142 cm−1 assigned to TiO2-anatase (O–Ti–O bending vibration) for F1P4K sample indicates the transformation of the amorphous form to anatase, as a result of the calcination process (Fig. 6b). Other anatase bands at 194 cm− 1, 393 cm− 1, 515 cm− 1 and 637 cm−1 [48] were not observed, because there are strong bands of basalt fibers in this range. The spectrum of F1P4K cross-section (Fig. 7c-II) shows that fibers have been modified only on the surface (the band at 142 cm−1). The spectrum in the middle of the cross-section is characteristic for raw basalt fibers (Fig. 7c-I). The spectrum of the F1P4K surface corresponds to basalt fibers and TiO2-anatase. TiO2 coatings are very thin and bands attributed to anatase are obscured by bands of the fibers. At each tested point of the fibers surface the TiO2-anatase form is observed (Fig. 7a, b — white points). The results of the Raman analysis for F3P4K and F5P5K are analogous to the ones described above for F1P4K sample (not shown). 3.4. XRD analysis XRD results for the thin TiO2 coating on the basalt fibers (Fig. 8a) confirm the formation of anatase structure after calcination at 500 °C. XRD spectrum shows the most intense reflection at (2θ) 25.31° corresponding to the (101) plane diffraction peak of anatase. Two less intense reflections at 2θ of 37.76°, 48.05° correspond to the (004) and (200) planes. Other anatase characteristic (211) and (204) planes at 2θ of 55.07° and 62.94° are not visible on XRD spectrum [19]. For raw basalt fibers any reflection characteristics for anatase were observed (Fig. 8b). 3.5. SEM/EDS analysis
Fig. 4. DSC analysis of a) basalt fibers with TiO2 coating before calcination and b) raw basalt fibers (F).
The SEM results of basalt fibers and Si wafers after surfactant decomposition are presented in Figs. 9 and 10. The substantial changes in the
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Fig. 5. FTIR/ATR spectra of a) CTAB powder, TiO2 modified basalt fibers with 1% CTAB (F1), TiO2 modified basalt fibers with 1% CTAB after calcination (F1K); TiO2 modified basalt fibers with b) 5% CTAB (F5) and F5 plasma treated for 1 h (F5P1), 2 h (F5P2), 3 h (F5P3), 4 h (F5P4), 5 h (F5P5); c) 3% CTAB (F3) and F3 plasma treated for 1 h (F3P1), 2 h (F3P2), 3 h (F3P3) 4 h (F3P4); d) 1% CTAB (F1) and F1 plasma treated for 1 h (F1P1), 2 h (F1P2), 3 h (F1P3), 4 h (F1P4).
surface topography are visible for the samples modified with CTAB. During CTAB removing, the porous structure of the TiO2 layer is formed, which depends on the amount of the surfactant.
Fig. 6. Raman spectra of a) raw basalt fibers (F), TiO2 modified basalt fibers with b) 1% CTAB plasma treated for 4 h and calcined (F1P4K), c) 1% CTAB plasma treated for 4 h (F1P4), d) 1% CTAB (F1) and e) CTAB powder.
Similar results were observed also by other scientists [11,49–51]. The higher content of the surfactant results in the formation of larger pores (and also a greater surface area of the pores) in the coatings. The TiO 2 coating on a Si wafer containing 5% CTAB has about five times larger surface area of the pores compared to the samples with 1% CTAB (Fig. 10c, d, g, h). The differentiation of the coating depending on the amounts of the added surfactant is also observed on the fibers (Fig. 9). The texture of the fiber coating has a different nature than that on the Si wafer (size, distribution and shape of the pores). This may be a result of the physico-chemical properties (chemical composition, roughness) and the shape of both types of substrate samples (Figs. 9 and 10). It has also been noted that the way of surfactant removing influences the morphology and texture of the obtained coatings, both in the case of fibers and wafers. The pore diameter of TiO 2/CTAB coatings measured for Si wafers only after the plasma treatment (not shown on SEM images) is bigger (37 ± 7 nm, 62 ± 8 nm and 113 ± 30 nm for 1%, 3% and 5% CTAB, respectively) compared to the results obtained for the same samples after the completion of the two-stage process (33 ± 7 nm, 56 ± 13 nm and 92 ± 29 nm, respectively) (Fig. 9c, e, g), and for the samples after the one-stage process (28 ± 5 nm, 37 ± 9 nm and 58 ± 22 nm, respectively) (Fig. 9d, f, h). The differentiation of the TiO 2 coating on fibers is the lowest for the sample with 1% CTAB (Fig. 10). The coating after the one-stage process (Fig. 10d) is
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Fig. 7. Raman point maps made for a) cross-section and b) surface of TiO2 modified fibers with 1% CTAB plasma-treated for 4 h and calcined (F1P4K) (white points — TiO2 anatase and black points — basalt fiber/lack of TiO2 and c) Raman spectra of F1P4K in the middle of fiber cross-section (I) and on fiber surface (II).
comparable to that after the two-stage process (Fig. 10c). On the basis of the F5K SEM image (Fig. 10h, j), the greatest effect of the surfactant addition is visible for the sample with 5% CTAB. However, the percentage of pores is larger for sample F5P5K, after the two-stage process (Fig. 10g, i). For 3% CTAB, larger structural changes of the coating were also observed for the two-stage process. It was found that calcination of the plasma-treated and untreated coatings resulted in a reduction and distortion of the pores. It may be caused by contractions (movements) of the coatings in the calcination process or
the gaseous products of the surfactant decomposition may change the structure of the coatings. The biggest surface area of the pores was found for TiO 2/5% CTAB coatings after the two-stage process (plasma treatment/calcination): 41% for Si wafer (W5P5K, Fig. 9g) and 33% for fiber (F5P5K, Fig. 10i). TiO2/5% CTAB coatings after the one-stage process (calcination) have a smaller surface area of the pores, namely 31% for Si wafers (W5K, Fig. 9h) and 28% for fibers (F5K, Fig. 10j). As mentioned above, the structures of the coatings on the fibers obtained with the same method differ significantly
Fig. 8. XRD spectra of a) 80 nm TiO2 coating on basalt fibers (F0) and b) raw basalt fibers (F).
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Fig. 9. SEM images of raw Si wafer (a), TiO2 coating (magnification 35,000× and 120,000×) without CTAB (b) and with CTAB on Si wafers (c–h). The percentage of the pore surface (A) and the distribution of the pore diameter (d).
compared to the coatings on the Si wafers. The thickness of these two layers differs also considerably and amounts to 20 nm for wafers and 80 nm for fibers. The results of the SEM/EDS analysis are presented in Fig. 11 and in Table 3. Raw basalt fibers contain traces of Ti 0.3 ± 0.1%, while for all TiO2 -modified samples, the Ti content is 2 ± 0.6%. The SEM/EDS results also show the presence of other elements,
which are components of raw basalt fibers. The content values of individual elements are similar, while a significant increase in the amount of carbon is noticeable for fibers with the TiO2 film (smooth and porous). This is probably related to the removal of residue isopropanol (present in the sol) and/or surfactant (for porous samples) the from TiO2 coating during annealing. The X-ray energy
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Fig. 10. SEM images of raw basalt fibers (a), TiO2 coating (magnification 35,000× and 120,000×) without CTAB (b) and with CTAB on basalt fiber surface (c–h). The percentage of the pore surface (A) for F5P5K (i) and F5K (j) fibers.
spectra for F1K or F1P4K collected from five points do not differ and Ti is evenly distributed on the tested fiber surface. This is confirmed by the maps of the Ti distribution (Fig. 11). 4. Conclusions The nano-layers of TiO 2 -anatase with various structures and thicknesses on the surfaces of basalt fibers (80 nm) and Si wafers (20 nm) using the sol–gel technique and different subsequent treatments were obtained. TiO2 sol samples without and with CTAB surfactant (1%, 3% and 5%) were tested. Two methods of surfactant removing were used: calcination only and low-temperature air plasma treatment with subsequent calcination. From the results of TGA and FTIR/ATR, it was found that CTAB is removed both in the plasma treatment process and during calcination. The decomposition rate of CTAB depends on the content of the surfactant and the time of plasma treatment. The TiO2 coatings obtained by the presented methods are evenly distributed on the fibers surface. The Raman results show that after calcination at 500 °C, TiO2 in the photocatalytically active form-anatase was obtained. The XRD analysis also confirmed the
presence of TiO2 anatase in the coating of basalt fibers, although the intensity of the band characteristic of anatase is low due to the very thin coating. The most intense reflection at (2θ) 25.31° corresponds to the (101) plane diffraction peak of anatase. The DSC analysis showed the transformation of amorphous TiO2 on the fibers to the anatase form in the range 435–472 °C and the exothermic nature of this process. The high thermal resistance of basalt fibers made it possible to carry out the calcination process directly on the fibers' surface. The results of the SEM analysis indicate changes in the surface topography of the samples with the surfactant addition. The plasma treatment before calcination resulted in a greater development of the TiO2 layer structure. The structure of TiO2 layers depends also on the type of the substrate. In the case of Si wafers, the pores have a shape close to circular and their diameter/surface area increases alongside an increase of the surfactant addition. For fibers, the formation of smaller, irregular, channel pores was observed. The greatest diversity of the TiO 2 coating structure was found for the 5% addition of CTAB. In further research, the obtained TiO2 coatings on basalt fabrics with various surface developments will be used in the photocatalysis process.
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Fig. 11. SEM/EDS analysis of TiO2 modified fibers with 1% CTAB a) calcined (F1K), b) 4 h plasma treated for 4 h and calcined (F1P4K) with maps of the Ti distribution on the fiber surface (white spots — Ti).
Table 3 Results of SEM/EDS analysis of raw basalt fibers (F), TiO2 modified fibers (F0), TiO2 modified fibers with 1% CTAB: 4 h plasma-treated and calcined (F1P4K); calcined (F1K). Sample
F F0 F1P4K F1K a b
Elemental content [weight %] C
O
Na
Mg
Al
Si
K
Ca
Ti
Fe
15.1a ± 0.8b 22.5 ± 3.7 24.26 ± 3.7 20.1 ± 3.3
49.7 ± 0.4 43.7 ± 3.5 43.7 ± 1.7 43.8 ± 3.3
2.7 ± 0.1 3.0 ± 0.4 2.0 ± 0.2 1.9 ± 0.8
2.5 ± 0.1 2.2 ± 0.2 1.3 ± 0.2 1.6 ± 0.3
5.9 ± 0.1 4.9 ± 0.2 5.1 ± 0.4 5.8 ± 0.6
16.7 ± 0.5 14.6 ± 0.4 15.2 ± 1.1 17.1 ± 1.6
0.6 ± 0.1 0.5 ± 0.1 0.8 ± 02 0.8 ± 0.2
3.2 ± 0.2 3.1 ± 0.3 2.9 ± 0.5 3.4 ± 0.4
0.3 ± 0.1 2.0 ± 0.5 2.3 ± 0.3 1.9 ± 0.3
3.2 ± 0.2 3.4 ± 0.5 2.5 ± 0.7 3.7 ± 0.5
The averaged values from five measurements. Standard deviation.
Acknowledgments The study was carried out within the Key Project — POIG.01.03.01-00004/08 Functional Nano- and Micro-textile Materials — NANOMITEX cofinanced by the European Union with the financial resources of the European Regional Development Fund and the National Centre for Research and Development within the framework of the Innovative Economy Operational Programme, 2007–2013, Priority 1. Research and development of modern technologies, Activity 1.3. Supporting R&D projects for enterprises undertaken by science establishments, Subactivity 1.3.1. Development projects. The authors would like to thank Mr Damian Batory from Institute of Materials Science and Engineering, Lodz University of Technology for the performance of the XRD analysis.
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