Ultraviolet shielding properties of cotton fabric supported by titanium-calcium hydroxyapatite solid solution particles

Abstract

Titanium-calcium hydroxyapatite (TiCaHap) particles were tried to be prepared by a wet method using starting solution with the ratio of Ti/(Ti + Ca) (denoted as [X_Ti]) from 0 to 1 and pure TiCaHap particles were obtained from the condition with [X_Ti] from 0 to 0.10. The particles were characterized by field emission scanning electron spectroscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy and spectrophotometry. Ultraviolet-visual (UV-vis) spectroscopy revealed that TiCaHap particles exhibit strong UV absorption under 380 nm. The UV absorption increased with an increase in concentrations of Ti⁴⁺. The TiCaHap prepared with [X_Ti] = 0.05 was supported on cotton fabric. The UV shielding ability of the cotton fabric was enhanced by the addition of the TiCaHap particles. The influences of pre-treatment using a cationizing agent and washing with water or a sodium dodecyl sulfate solution for the cotton fabrics were also discussed.

Keywords

ultraviolet shielding ability cotton fabric hydroxyapatite titanium ion calcium ion

The hydroxyapatite (Hap) structure, Me₁₀(PO₄)₆(OH)₂, is very tolerant to ionic substitutions. Therefore, the Me site can be occupied by various divalent cations (Ca²⁺, Mg²⁺, Sr²⁺, Cd²⁺, Pb²⁺ and Ba²⁺),^1–9 by some trivalent cations (Cr³⁺, Al³⁺ and Fe³⁺)^10,11 and by the quadrivalent cation (Ti⁴⁺).^12,13 Calcium hydroxyapatite (CaHap), Ca₁₀(PO₄)₆(OH)₂, is a major inorganic component of hard tissues in animals.^1,2,14 The substitution of Ca²⁺ in CaHap with other metal ions strongly affects the characteristics of the particles, including the size, crystallinity, solubility, thermal stability, surface characteristics and adsorptive activity.¹⁵

A solid solution is a solid-state solution of one or more solutes in a solvent.¹⁶ We synthesized various Hap solid solution particles involving Ca²⁺ and other cations into cation sites of the Hap crystal and reported their composition and structures in previous studies.^5–9,17,18 We revealed in these studies that strontium-calcium hydroxyapatite (SrCaHap)⁶ and cadmium-calcium hydroxyapatite (CdCaHap)⁷ can be prepared from solutions across the whole range of Me/(Me + Ca) atomic ratios (denoted as [X_Me]) from 0 to 1, whereas magnesium-calcium hydroxyapatite (MgCaHap),⁵ lead-calcium hydroxyapatite (PbCaHap),⁸ barium-calcium hydroxyapatite (BaCaHap)⁹ and yttrium-calcium hydroxyapatite (YCaHap)¹⁸ can be formed only over a limited range of [X_Me]. Nine types of lanthanoid could be incorporated into lanthanoid-calcium hydroxyapatite (LnCaHap, Ln = La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Gd³⁺, Dy³⁺, Er³⁺ and Yb³⁺), but they were present at less than 0.01–0.03%.^17,18 From these studies, it is suggested that Hap can be utilized as a host material by accumulating metal ions into its crystal structure.

Ultraviolet (UV) rays are implicated as the major cause of DNA damage, skin cancers, sun burn, suntan, cataracts, wrinkles and so on.¹⁹ UV rays adversely affect humans. Therefore, it is necessary for us to be protected from UV rays. Cerium oxide (IV) is known to absorb UV light.^20,21 It is reported that cerium-calcium hydroxyapatite (CeCaHap) also has this UV-absorption capability.^17,22 Titanium oxide (IV) is also known to be a UV absorber^23–32 and it is used in suntan lotion to protect skin²⁴ and in cosmetic applications.²⁵ The composite of zinc oxide (ZnO) and TiO₂^26–28 and the composite of silver (Ag) and TiO₂²⁹ are also used as UV absorbers. TiO₂³⁰ and the composite of TiO₂ and polyvinylsilsesquioxane³¹ were supported on cotton fabric and the UV protecting blocking ability of the cotton was investigated. The composite of TiO₂ and CaHap was also studied.³² The characteristics of titanium-calcium hydroxyapatite (TiCaHap) particles, including the size, crystallite sizes and UV-absorption properties, were studied, but the particles were never supported on fabric.^12,13

Therefore, we have prepared TiCaHap solid solution particles in this study. Then, we examined the influence of Ti⁴⁺ ions on the composition and structure of the resulting particles using various techniques. The UV-absorbing ability of TiCaHap prepared with different Ti⁴⁺ contents was investigated and compared to CeCaHap synthesized in a previous study.^17,22 The obtained TiCaHap particles were supported on cotton fabric, and the UV shielding properties of the treated fabrics were investigated. The influence of washing the supported fabric was also studied. Moreover, the influence of pre-treatment of cotton fabric was also investigated.

Materials and methods

Preparation of TiCaHap particles

TiCaHap particles with various Ti/(Ti + Ca) atomic ratios were synthesized by the following precipitation method based on previous reports.^5,6 Solutions of 1.6 dm³ with different Ti/(Ti + Ca) ratios were prepared by mixing various amounts of Ca(OH)₂ and 30% Ti(SO₄)₂ solutions in deionized and distilled water free from CO₂ under a N₂ atmosphere. The total moles of Ti⁴⁺ and Ca²⁺ in the starting solution were kept constant at 32 mmol, and the Ti/(Ti + Ca) atomic ratios in the solutions (denoted as [X_Ti]) were 0, 0.01, 0.03, 0.05, 0.10, 0.20, 0.40, 0.50, 0.60, 0.80 and 1. The solutions were stirred at room temperature for 1 h and then a diluted solution of H₃PO₄ (19.2 mmol) was added while stirring. The (Ti + Ca)/P atomic ratio was adjusted to 1.67, which was the stoichiometric ratio in Hap. The solution pH was adjusted to 9.50 by the addition of NH₄OH when it was lower than 9.50. The resulting suspension was stirred at room temperature for 1 h and then aged in a 2 dm³ screw-capped polypropylene vessel at 100℃ for 48 h. The resulting precipitates were filtered out, washed in 1 dm³ of deionized distilled water and finally dried in an air oven at 70℃ for 16 h.

All chemicals were reagent grade, were supplied by Wako Chemical Co. and were used without further purification.

Fabric and supporting particles on fabric

Plain woven fabric, specifically “Kanakin (unbleached muslin) #3,” supplied by the Japan Standard Association, was chosen as the sample substrate for this study. The structure was as follows: the pick count was 31/27 (pick/cm) for warp/weft, the weight was 106 g/m² and the thickness was 0.23 mm. The fabric was washed in distilled boiling water for 10 min twice and dried naturally in the laboratory before being used to support the particles.

Particle embedding was performed using a beaker (0.3 dm³) according to the previous study.²² A 10 cm³ 1:1 mixture of ethanol and water was used as the dispersion medium. TiCaHap particles prepared with [X_Ti] = 0.05 were used for fabric support studies. The volume of the dispersion medium was 10 cm³. The concentrations of the dispersion medium were 1, 5, 10 and 20 g/dm³. The dispersion medium was irradiated with ultrasonic waves for 3 min. A piece of cotton fabric (50 × 50 mm²) was immersed into the dispersion medium and the beaker was shaken at 25℃, 60 spm for 30 min. After the particle supporting process, the fabric was washed in water twice, dried under ambient conditions and then kept in a desiccator.

The washing test was performed on the fabric supported with particles as follows. The fabric was immersed in water (10 cm³) or a solution (10 cm³) containing sodium dodecyl sulfate (SDS) (8 mmol/dm³) and shaken at 25℃, 60 spm for 15 min using a beaker (0.3 dm³). After washing, the fabric was rinsed with water and dried in the laboratory. This process was repeated one or two or three times.

Pre-treatment to cationize cotton fabric

TiCaHap particles were also supported on cotton fabric that was cationized as a pre-treatment before the particle embedding addition to the fabric without any pre-treatment. The method of cationizing the cotton fabric was as follows. A cationic polymer DANSHADER®-185 (Nittobo Medical Co., Ltd, Japan) was used as a cationizing agent. A solution containing the cationizing agent was prepared. The concentration and the volume of the solution were 10.0 g/dm³ and 10 cm³, respectively. A piece of cotton fabric (50 × 50 mm²) was immersed into the solution (bath ratio 1:30) and treated at 75–80℃, 600 rpm for 20 min using a hot stirrer. Then, 0.3 g of sodium carbonate (Na₂CO₃) were added into the solution and the treatment was continued at 75–80℃, 600 rpm for 30 min. The fabric was rinsed with water twice and dried in the laboratory.

Characterization

The particles synthesized in this study were characterized by the following methods. The crystal phase was analyzed using powder X-ray diffraction (XRD, Rigaku Geigerflex 2013) with Ni-filtered CuKα radiation (30 kV, 15 mA). The crystallite sizes of the particles were evaluated using the Scherrer equation³³ and the half-height width of the XRD peaks at 2θ = 25.9°, due to the (002) plane, and at 2θ = 32.9°, due to the (300) plane. The particle morphology was observed with field emission scanning electron spectroscopy (FE-SEM, JEOL JSM-7000F) at an accelerating voltage of 10 kV. The atomic composition of the particles, including Ti and Ca content, was obtained using energy-dispersive X-ray spectroscopy (EDS, JED-2300) attached to the field emission scanning electron spectroscope at an accelerating voltage of 20 kV. Diffuse reflection ultraviolet-visual (UV-vis) spectra of the particles were obtained using an UV-vis spectrophotometer (Jasco V-670ST) between 260 and 800 nm with an integrating sphere (ISV-722).

The cotton fabrics before and after particle support were characterized by XRD and FE-SEM using similar methods to the particle characterization mentioned above. The atomic compositions of C, O, Ti, Ca and P of the fiber surface were measured using EDS, as mentioned above. Transmission UV-vis spectra of various fabrics were measured using the same apparatus mentioned above. The Ultraviolet Protection Factor (UPF) was obtained using a program (Jasco VWUP-712) installed into the UV-vis system. This measurement was based on ISO 24444:2011.³⁴

Results and discussion

Morphology

Figure 1 presents FE-SEM images of the particles obtained at [X_Ti] = 0–1. The particles formed with [X_Ti] = 0–0.40 were fine ellipsoidal particles. However, the long rod-like particles were mixed with the fine irregular particles at [X_Ti] = 0.5–0.6. Fine irregular particles were formed under the conditions of [X_Ti] = 0.8–1.

Figure 1.

Field emission scanning electron spectroscopy images of the obtained particles.

The mean particle length and width of the particles obtained at [X_Ti] = 0–0.4 were estimated from the FE-SEM images and shown by open circles and open squares, respectively, as a function of [X_Ti] in Figure 2. The particles with [X_Ti] = 0 were 65.9 ± 22.1 nm in length and 21.8 ± 4.7 nm in width. When [X_Ti] increased to 0.01 the particle length increased, at [X_Ti] = 0.01–0.05 the particle length decreased and at [X_Ti] > 0.05 it increased again. The changes could be classified into two: the existence of a maximum of the particle length at [X_Ti] = 0–0.05 and the increase of the particle length at [X_Ti] > 0.05. Firstly, regarding the maximum at [X_Ti] = 0–0.05, similar results were observed with LnCaHaps, which were prepared with Ln/(Ln + Ca) = 0–0.15.^16,17 The incorporation of cations other than Ca²⁺ ions and the crystal growth of solid solution particles were considered to affect the change of the particle length. Secondly, the particle length increased at [X_Ti] > 0.05. In contrast, the mean particle width gradually decreased to ca. 15 nm, and the overall size change was small. A similar increase of the particle length was observed in a series of SrCaHaps and the adsorption of proteins³⁵ and acetic acid³⁶ onto CaHap. When protein³⁵ and acetic acid³⁶ adsorbed on the rod-shaped CaHap particles, they adsorbed to the side plane (a- and/or b-axis directions) of the particles. Then, the crystal growth along the (a00) plane was inhibited by them and the crystal grew along the (00 c) plane. It is considered that Ti⁴⁺ ions also inhibit the crystal growth of the side plane of the TiCaHap in the present study.

Figure 2.

Plots of mean particle sizes (○,□) and crystallite sizes (•,▪) of obtained particles versus [X_Ti]. ○: particle length; □: particle width; •: crystallite size due to (002) plane; ▪: crystallite size due to (300) plane.

Crystal structure and crystallinity

The crystal phases of the obtained particles were determined by XRD. Figure 3 shows the XRD patterns of the particles obtained at [X_Ti] = 0–1. The particles formed with [X_Ti] = 0 were identified as CaHap (JCPDS 9-432). No peaks other than Hap were found for the particles formed with [X_Ti] = 0.01–0.60. The particles formed with [X_Ti] = 0.80–1 were amorphous. The base lines of XRD patterns of the TiCaHap particles increased with an increase of [X_Ti], although it cannot be seen from this figure. From the results of XRD, pure Hap seems to be prepared with [X_Ti] = 0–0.60. These results will be discussed further in the Lattice parameters section.

Figure 3.

X-ray diffraction patterns of the obtained particles.

The crystallite sizes of the particles were evaluated from the XRD peaks (Figure 3) due to the (002) plane and (300) plane. The results are shown by closed symbols as a function of [X_Ti] along with the particle length and width in Figure 2. The crystallite sizes obtained based on the (002) plane (•) and the (300) plane (▪) of TiCaHap particles produced at [X_Ti] = 0 were 71 and 24 nm, respectively. With increasing [X_Ti], the crystallite size due to the (002) plane variedly changed and the size due to the (300) plane slightly decreased to 16 nm. The crystallite size due to the (002) and the size due to (300) plane showed near values with the particle length (○) and width (□), respectively, at [X_Ti] = 0–0.10. Therefore, the TiCaHap particles with [X_Ti] ≤ 0.10 were regarded as single crystals and the particles with [X_Ti] ≥ 0.20 were regarded as polycrystalline.

Ti⁴⁺ and Ca²⁺ content

The Ti⁴⁺ and Ca²⁺ content of the particles were obtained. Ti/(Ti + Ca) and Ca/(Ti + Ca) atomic ratios in the particles are plotted against [X_Ti] in the starting solution in Figure 4. The Ti/(Ti + Ca) ratio (○) increased and the Ca/(Ti + Ca) ratio (□) decreased with an increase of [X_Ti]. This confirmed that Ti⁴⁺ ions added to the synthesis solution are incorporated into the particles.

Figure 4.

Ti (○, •) and Ca (□) contents in particles versus [X_Ti] in starting the solution.

In addition, the Ti/(Ti + Ca) and Ca/(Ti + Ca) atomic ratios differ between the long rod-like particles and the fine particles based on the morphology for the particles with [X_Ti] = 0.6 (Figure 1). The average Ti/(Ti + Ca) atomic ratio was 0.60 (○) and the average Ca(Ti + Ca) atomic ratio was 0.40 (□). On the other hand, the Ti/(Ti + Ca) ratio of the long rod-like particles was 0.07 (•) and the Ti/(Ti + Ca) ratio of the fine irregular particles was 0.85 (•). These four symbols are shown at [X_Ti] = 0.6 in Figure 4. From these results, Ca²⁺ ions are maldistributed in the long particles and Ti⁴⁺ ions are maldistributed in the fine irregular-shaped particles.

Lattice parameters

Lattice parameters a and c were obtained from the XRD peaks due to the (300) and (002) planes, respectively, for the particles obtained at [X_Ti] = 0–0.40. The results of parameters a and c are shown by circles and squares, respectively, against [X_Ti] in Figure 5. The parameters a and c of CaHap with [X_Ti] = 0 were 0.945 and 0.690 nm, respectively. Both the parameters decreased with increasing [X_Ti] from 0 to 0.05, as shown by closed symbols. This is because larger Ca²⁺ ions (ionic radius: 0.100 nm) were replaced by smaller Ti⁴⁺ ions (0.061 nm).³⁷ However, both parameters gradually increased to a size similar to that of CaHap at [X_Ti] = 0.05–0.40. This result showed that Ti⁴⁺ ions were difficult to incorporate into the Hap structure at [X_Ti] ≥ 0.10.

Figure 5.

Lattice parameters a (○, •) and c (▪, □) versus [X_Ti].

From the results of Figures 1–5 and the discussion, it is believed that Ca²⁺ and Ti⁴⁺ ions are incorporated into the TiCaHap structure, the pure TiCaHap single crystal can be prepared at [X_Ti] = 0–0.10 and Ti⁴⁺ ions are difficult to incorporate into the Hap structure at higher [X_Ti]. It is believed that the particles with [X_Ti] = 0.20–0.40 are a mixture of fine ellipsoidal-shaped CaHap and amorphous particles containing Ti⁴⁺ ions, and the particles with [X_Ti] = 0.50 and 0.60 are a mixture of long rod-like CaHap and fine irregular amorphous particles containing Ti⁴⁺ ions.

UV-vis spectra

The diffuse reflection UV-vis spectra of the particles prepared with various [X_Ti] are shown in Figure 6. CaHap particles with [X_Ti] = 0 never exhibit strong UV absorption. In contrast, the reflection of the spectra by the particles containing Ti⁴⁺ ions decreased remarkably in the UV range below 380 nm. This UV absorption clearly increased with an increase in Ti⁴⁺ content at [X_Ti] ≤ 0.05, but no apparent changes are shown at [X_Ti] ≥ 0.05.

Figure 6.

Diffuse reflection ultraviolet-visual spectra of the obtained particles with different [X_Ti].

It was reported in a previous study that the light absorption of CeCaHap decreased in the UV range under 400 nm.^17,22 In a comparison between TiCaHap and CeCaHap, it is revealed that TiCaHap is a stronger UV absorber than CeCaHap under 320 nm, but CeCaHap absorbs more light than TiCaHap between 320 and 400 nm.

Supporting of particles on fabric

TiCaHap particles prepared with [X_Ti] = 0.05 were supported on cotton fabric. Figure 7 shows transmission UV-vis spectra of the fabric before and after the addition of particles with different concentrations of dispersion ranging from 1 to 20 g/dm³. The fabric before the particle support showed comparatively higher light transmittance (43–45%) across 260–800 nm, although the spectra in the range from 500 to 800 nm are not shown here. In contrast, the fabrics supported by the particles exhibit lower transmittance in the UV range under 360 nm; that is, the fabrics have UV shielding ability. This ability becomes stronger by increasing the concentration of the dispersion. This trend becomes saturated and levels off at concentrations ≥10 g/dm³.

Figure 7.

Transmission ultraviolet-visual spectra of cotton fabrics before and after the addition of titanium-calcium hydroxyapatite particles with [X_Ti] = 0.05 at different concentrations of 1-20 g/dm³.

Figures 8(a)–(e) depict FE-SEM images of the cotton fabrics before and after the particle support with different concentrations of the dispersion. Before the addition of particles (a), the fibers are wrinkled, which is a characteristic of cotton. As the particle concentration increases, the fibers are wholly covered by the fine particles and the wrinkles of the cotton are filled by the particles. The amounts of C, O, Ti, Ca and P on the surfaces of the fibers are also shown in Figure 8. The atoms derived from TiCaHap (Ti, Ca and P) are detected on the fiber after the support, and the ratios increase with an increase in the concentration of the dispersion. From these figures, the particles seem to be excessively and heterogeneously supported on the fibers at a concentration of 20 g/dm³. Therefore, it can be said that the suitable dispersion concentration is 10 g/dm³, based on the results in Figures 7 and 8.

Figure 8.

Field emission scanning electron spectroscopy pictures of various fabrics and atomic ratios on the surfaces: (a) before support; (b)–(e) supported by titanium-calcium hydroxyapatite at various concentration of dispersion; (f), (g) supported at 10 g/dm³ and washed in water (f) or a sodium dodecyl sulfate solution (g).

The UPF value of the cotton fabric before treatment was 2.1. The UPF value of the fabric after the particle support with 10 g/dm³ increased to 7.3. The cotton fabric used in this study was relatively thin. Therefore, the UPF values of the folded fabric were also measured. The UPFs of the fabric (two ply) before and after the particle support were 13.9 and 29.8, respectively. Thus, the UV shielding ability of cotton fabric was enhanced by the supporting of TiCaHap particles.

Figure 9 shows XRD patterns of cotton fabric before support (b) and the fabric supported by the particles at 10 g/dm³ (c) along with the patterns of the particles (a). The pattern of the particles (a) is the same as the pattern shown in Figure 3 ([X_Ti] = 0.05.) The appearance of a small peak shown by a triangle mark in pattern (c) agrees with the strongest peak of the particles (a). Therefore, it was confirmed that TiCaHap particles were supported on cotton fabric.

Figure 9.

X-ray diffraction patterns of cotton fabrics and particles: (a) titanium-calcium hydroxyapatite particles with [X_Ti] = 0.05; (b) cotton fabric before support and (c) cotton fabric after support by the particles at 10 g/dm³.

Influence of washing

The fabric treated with 10 g/dm³ of particles was washed twice in water or a SDS solution of 8 mmol/dm³ in order to investigate the influence of washing. The FE-SEM images and atomic ratios of the surfaces of the fabric are shown in Figures 8(f) and (g). The atomic ratios of Ti, Ca and P, which come from TiCaHap particles, decreased compared with the ratios of the fabric before washing (d). However, the final analysis still shows the presence of particles on the fabric after washing.

Figure 10(a) shows the UV-vis spectra of the cotton fabrics supported by TiCaHap before and after washing in water and a SDS solution twice. The spectrum of the fabric before supporting particles is also shown in this figure. The UV shielding ability becomes weakened by washing in water or a SDS solution compared with the sample before washing. Figure 10(b) shows the UV-vis spectra of the fabrics supported by the particles before and after washing in water from one to three times. It can be said that the ability becomes weakened by washing once, but no apparent changes were shown by the washing from one to three times. A similar tendency was obtained for washing by a SDS solution, although the spectra are not shown here to avoid complication. Therefore, the fabric partly retains its ability to shield UV rays even after washing for cotton fabric without any pre-treatment. The particles and the fabric first interacted electrostatically, after which the particles entered into the wrinkles of the cotton fibers and the slits among the cotton fibers.

Figure 10.

Transmission ultraviolet-visual spectra of various cotton fabrics before and after the support of titanium-calcium hydroxyapatite particles and washing: (a) and (b) without pre-treatment; (c) with cationization; (a) and (c) washed in water or a sodium dodecyl sulfate (SDS) solution twice; (b) washed in water once, twice and three times.

Influence of cationizing treatment

The effect of pre-treatment using a cationizing agent on the cotton fabric on the UV shielding ability was investigated. Because the surface of TiCaHap was negatively charged,³⁸ cationizing the cotton fabric was expected to cause electrical attraction between the fabric and the particles, and enhance the UV shielding ability of the fabrics supported by the particles.

Figure 10(c) shows the UV-vis spectra of the fabrics supported by TiCaHap with pre-treatment using a cationizing agent before and after washing twice. The UV shielding ability of the fabrics supported by TiCaHap particles before washing was enhanced by the cationization a little, as shown by broken lines in Figures 10(a) and (c). The pre-treatment enhanced the UV shielding ability of the fabrics after washing very well. It can be said that cationization hardly desorbs the particles from the cotton fabric and maintains the UV shielding ability of the fabric.

The Ti⁴⁺ ions used in the present study have a UV shielding ability. There are many other metals that have valuable properties, for example, luminescence, magnetism and antibacterial properties. If various metal-calcium hydroxyapatite solid solution particles are prepared and can be arbitrarily supported on various fabrics, new high-performance textile fabrics can be made in the future.

Conclusions

TiCaHap particles were prepared by a wet method at different [X_Ti]. The particles obtained at [X_Ti] = 0–0.10 were considered to be pure TiCaHap from the results of various assessments. The particle length was sensitive to a change in Ti⁴⁺ content; in contrast, the particle width was almost constant. With increasing Ti⁴⁺ content, the crystallinity and lattice parameters a and c of the particles decreased and the UV absorption under 380 nm was enhanced. The UV-absorption range differs between TiCaHap and CeCaHap. The cotton fabric supported by TiCaHap particles had sufficient UV shielding ability. The properties was enhanced by cationizing of the cotton fabric. The properties was maintained enough after washing in water or a SDS solution.

Footnotes

Declaration of conflicting interests

The authors declared no potential conflicts of interest with respect to the research, authorship and/or publication of this article.

Funding

The authors disclosed receipt of the following financial support for the research, authorship and/or publication of this article: This work was supported in part by JSPS KAKENHI (Grant No. 18K02201).

ORCID iD

Akemi Yasukawa

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Ultraviolet shielding properties of cotton fabric supported by titanium-calcium hydroxyapatite solid solution particles

Abstract

Keywords

Materials and methods

Preparation of TiCaHap particles

Fabric and supporting particles on fabric

Pre-treatment to cationize cotton fabric

Characterization

Results and discussion

Morphology

Crystal structure and crystallinity

Ti4+ and Ca2+ content

Lattice parameters

UV-vis spectra

Supporting of particles on fabric

Influence of washing

Influence of cationizing treatment

Conclusions

Footnotes

Declaration of conflicting interests

Funding

ORCID iD

References

Ti⁴⁺ and Ca²⁺ content