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Cellulose

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Formaldehyde-free, crease-resistant functionalization of cellulosic material modified by a hydrolyzed dicarboxylic acid based alkoxysilane/melamine finishing system

  • Christian SchrammEmail author
  • Angelika Amann
Open Access
Original Research
  • 173 Downloads

Abstract

Cotton fabrics show the tendency to wrinkle. Various chemical agents have been used to convey crease-resistance to cellulosic material in an attempt to replace the formaldehyde-releasing crosslinking agent DMDHEU. A novel non-formaldehyde organic–inorganic hybrid material synthesized via the sol–gel route is investigated. The hydrolyzed trialkoxysilane (3-triethoxysilylpropyl)succinic anhydride was reacted with 2,4,6-triamine-1,3,5-triazine (melamine, MEL) at elevated temperature. The as-prepared aqueous solutions were applied to cotton fabrics, which were cured at 160 °C and 220 °C. The physicomechanical data: dry crease recovery angle (DCRA), flexural rigidity, whiteness index (WI), water retention, water vapor permeability were evaluated. An increase in the DCRA can be observed. However, the thermal treatment results in a reduction of the WI. Fourier transform infrared spectroscopy spectra confirm the formation of an imide group. X-ray powder diffraction analysis makes evident that the crystallinity index increased. SEM images make evident that depositions can be observed on the surface.

Graphical abstract

Keywords

Cotton Crease-resistance Polyimide Organic–inorganic hybrid Sol–gel 

Introduction

Cellulose-based material has been widely applied in many areas, since cellulose is regarded to be the most abundant biomass material and it also possesses various interesting properties, such as good mechanical strength and excellent hydrophilicity (Hearle 2002; Moon et al. 2011). The anhydroglucose unit of cellulose has three hydroxyl groups. Therefore, chemical modifications with practical relevance can be exclusively performed on these hydroxyls (Pinho and Soares 2018; Roy et al. 2009). Various attempts have been undertaken to chemically or physically modify the cellulose-based textiles to impart novel properties to the material (Bajaj 2002; Harifi and Montazer 2012; Mahbubul Bashar and Khan 2013; Paul 2015), such as improved antimicrobial activities (Arık et al. 2017; Brzezinski et al. 2007; Montazer and Afjeh 2007), enhanced flame-retardant properties (Alongi et al. 2011; Katovic et al. 2012; Lam et al. 2011b), improved hydrophobicity (Pipatchanchai and Srikulkit 2007; Zhang and Wang 2013), or better ultraviolet protection (Gambichler et al. 2001; Wang et al. 2011; Zheng et al. 2011).

The application of cotton is limited because of its tendency to produce creases. This fact can be attributed to the phenomenon that cellulose chains within the cotton fibers are held in place by intermolecular hydrogen bonds which are formed between the hydroxyl groups of adjacent molecules. Under the influence of deformation or moisture the hydrogen bonds are broken and reformed at a new location. To minimize this phenomenon crosslinking between the cellulose chains are formed applying various chemical agents.

Amongst these, the N-methylol compound DMDHEU (dimethyloldihydroxyethyleneurea) is the most effective and low cost crosslinking agent (Lam et al. 2011a; Trask-Morell et al. 1996; Yamamoto 1982). However, DMDHEU tends to release the potential human carcinogen formaldehyde (Hewson 1994; Kottes Andrews and Trask-Morell 1996). Consequently, various di- or polyfunctional crosslinking agents that do not emit formaldehyde were tested as a potential substitute for DMDHEU. Dialdehydes (Choi et al. 1999; Frick and Harper 1984; Vail and Arney 1971), isocyanates (Hobart and Mack 1969; Tomasino et al. 1982; Yeqiu et al. 2005), epoxides (Muresan et al. 2013; Reinhardt et al. 1961; Steele 1961), divinylsulphones (Rowland and Brannan 1970; Tesoro et al. 1961), and polycarboxylic acids (Schramm and Rinderer 2006; Welch 1994; Welch and Andrews 1989; Yang and Wang 1998) were thoroughly investigated.

The sol–gel technology is an excellent technique for chemical modification and functionalization of different surfaces. Therefore, it is a possible alternative approach to impart non-formaldehyde crease-resistant properties to cellulose-based textiles. The sol–gel process is based on the hydrolysis and the condensation reaction of metal alkoxides, such as tetraalkoxysilanes Si(OR)4, or organotrialkoxysilanes R1Si(OR2)3. As a consequence, three dimensional siloxane networks are formed with sizes in the nanometre range, which can be applied to the cellulosic material (Brinker and Scherer 1990; Hench and West 1990; Wright and Sommerdijk 2001). Thus, novel properties were conveyed to cellulosic material using the sol–gel process (Mahltig and Textor 2008).

Various investigations deal with the application of the sol–gel technique to impart wrinkle-free properties to cellulosic materials. The application of polycarboxylic acids in combination with tetraethoxysilane and (3-glycidyl)trimethoxysilane resulted in excellent durable press performance (Huang et al. 2007; Schramm et al. 2004, 2005; Zheng et al. 2011). Enhanced wrinkle resistance could also be obtained by thermal treatment of a cotton fabric having been impregnated with a solution containing GPTMS and aluminium isopropoxide (Schramm and Rinderer 2015, 2017). The sol–gel process was also applied to hemp fabrics to improve the crease-resistant properties (Arık et al. 2018).

When cotton specimens were impregnated with a solution containing hydrolysed (3-amino)propyltriethoxysilane and 1,2,3,4-butanetetracarboxylic acid and cured at elevated temperatures a polyimide was formed that improved the crease resistance of the cotton fabric (Schramm et al. 2014).

The objective of the present study was to investigate the reaction of hydrolyzed TESP-SA containing two carboxylic groups with melamine possessing three amino groups. The reaction of the carboxylic groups with the amino groups results in the formation of a poly(amic) acid which is applied to the cotton specimens. The thermal treatment at 220 °C results in the formation of a polyimide unit being component of an organic–inorganic composite covering the surface of the cotton sample. Since this novel finishing system never has been applied to a textile material it was of high interest to evaluate the mechanical and morphological properties of the finished cotton specimen.

Experimental

Materials

Desized, scoured, bleached and mercerized 100% cotton fabric, weighing 109 g/m2, was used throughout the investigation. (3-Triethoxysilylpropyl)succinic anhydride (100%, TESP-SA, Fig. 1) was obtained from Wacker Silicone, Burghausen, Germany. 2,4,6-Triamine-1,3,5-triazine (> 99%, melamine, MEL) (Fig. 1), hydrogen peroxide (35%), sodium silicate (10.6% Na2O, 26.5% SiO2) were purchased from Sigma Aldrich, Vienna, Austria. Deionized water was used throughout the investigation. The chemicals were used without further purification.
Fig. 1

Chemical formula of substances of interest

Preparation of the finishing solutions

Hydrolysis of TESP-SA

The standard procedure for the synthesis of a TESP-SA/MEL solution (molar ratio 1/1) in an aqueous medium was as follows: TESP-SA (8.37 mL, 30 mmol) was hydrolysed with HCl (c = 0.05 mol/L, 2.70 mL) in deionized water (30 mL) under magnetic stirring (500 rpm) in a polyethylene beaker (100 mL) for 2 h at room temperature (RT).

Solution of TESP-SA/MEL

3.78 g Melamine (30 mmol) were placed in a 500 mL three necked round bottom flask equipped with a reflux condenser, a dropping funnel and a magnetic stirrer. 80 mL of deionized water were added and the reaction mixture was heated until reflux. The hydrolyzed TESP-SA solution was transferred into the dropping funnel and added dropwise within 20 min under stirring. Subsequently, the reaction mixture was refluxed for 30 min. All solutions were adjusted to 150 mL final volume by adding water. In all cases clear solutions were obtained.

Finishing of the cotton fabrics

The pre-weighed cotton fabrics were impregnated with the corresponding TESP-SA/MEL solution by immersing the cellulosic material into the finishing bath for 10 min. The specimen was removed and treated with a two-roll laboratory padder (HVL 500 Mathis AG, Niederhasli, Switzerland; air pressure 1 bar, rotary speed 3 m/min). After drying (5 min, 105 °C) the as-treated fabric was cured in a lab dryer (LTE, W. Mathis AG, Switzerland) at a specified temperature (160 °C and 220 °C) for 15 min.

Bleaching of the cotton fabrics

A different solutions consisting of hydrogen peroxide were used to bleach the treated cotton fabrics. The bleaching bath 1 contained 4 g/L H2O2, 5 g/L sodium silicate and 2 g/L sodium hydroxide (38°Bè), whereas bleaching bath 2 contained twice the amount of hydrogen peroxide. The liquor ratio was 1:40. Sodium silicate was applied as a stabilizer for H2O2, and sodium hydroxide controlled the pH of the solution (pH = 10.0). The fabrics were heated for 1 h at 80 °C, rinsed with water and dried at 105 °C for 5 min.

Testing methods

The add-on values of the cotton samples were calculated as follow: add-on (%) = [(W2 − W1)/W1] × 100; W1 and W2 are the weights of the fabric specimens before and after treatment, respectively.

Dry crease recovery angle (DCRA) was measured according to ISO 2312: 10 test specimens were creased and compressed under controlled conditions of time and load. After removal of the creasing load the angle formed between the two limbs was measured. The DCRA values render possible the evaluation of a crosslinking reaction between a durable press finishing agent and the cellulosic material.

The stiffness of the fabrics was determined by means of a Taber Stiffness Tester, Model 112, New York, USA according to ASTM D 1388-R6. The flexural rigidity was calculated as described in ASTM D 1388-R6.

The measurement of the air permeability was conducted according to DIN EN ISO 9237 using the air permeability tester Textest FX 3030 LDM, Textest Ltd., Zurich, Switzerland. The air flux (L/dm2/min) that passes through the fabric was evaluated at a pressure difference of 100 Pa.

Colorimetric data measurements were conducted with the Spectrophotometer CM-3610d from Konica Minolta, Japan. The color data software CM-S100w Spectra Magic NX V1.9 was used for data acquisition. The whiteness index (WI) was calculated according to CIE.

Water retention value (WRV) was measured on dried samples which were allowed to swell in DI at room temperature for 2 h. Subsequently, the samples were centrifuged for 20 min at 3000 rpm. After the centrifugation process the samples were weighed (W2) and dried for 4 h at 105 °C and reweighed (W1). The WRV was calculated according following equation: WRV (%) = [(W2 − W1)/W1] × 100. The water vapor permeability (WVP) was studied gravimetrically by placing disks covered with the cellulosic specimens in a desiccator (air humidity 100%, 23 °C) for 96 h. The WVP rate was measured gravimetrically using the water method, following ASTM E96. A plastic cup (4 cm diameter, 2.5 cm height, 25 mL) was partially filled with DI (11 mL). A hole (1.5 cm diameter) in the lid of the cup was sealed with the circular test specimen. This cup assembly was placed in a desiccator filled with silica gel. An initial weight was taken of the assembly and was reweighed after 96 h.

SEM micrographs were recorded with an electron micro probe analyzer—JEOL JSM-6010LV. An acceleration voltage of 15 kV was used. The fibers were sputter-coated with a layer of gold. FT-IR/ATR spectra were recorded with a Bruker Vector 22 spectrometer using a DTGS detector. The spectra were the result of 50 scans. The spectral resolution was 4 cm−1. A PIKE MIRacle TM ATR accessory equipped with a diamond ATR crystal was used.

A Bruker-AXS D8 was used for X-ray powder diffraction (parallel beam optics, Cu-target, E-dispersive counter, sampler changer with rotation). The samples were run with 40 kV, 40 mA, 2°–60° θ/2θ, 0.01° step size and 5 s counting time. The crystallinity index (CrI) was calculated from the diffracted intensity data according to method of Segal et al. (French and Santiago Cintrón 2013; Ju et al. 2015). The calculation followed equation CrI = (I200 − Iam)/I200 × 100, where, I200: is the maximum intensity of the diffraction from (200) plane at 2θ = 22.8° and Iam: is the intensity of the amorphous back-ground scatter measured at 2θ = 18.0°.

Results and discussion

The stable triazine ring of melamine contains three reactive amino groups in 2, 4 and 6 position. Therefore, melamine is capable of undergoing various reactions (Bann and Miller 1958). The most important reaction is the methylolation of the amino groups by means of formaldehyde resulting in the formation of a melamine resin, a durable thermosetting plastic (Fink 2005). The amine group of melamine also can be acylated at elevated temperatures by means of anhydrides or amides (Bann and Miller 1958).

Thus melamine was reacted with hydrolyzed TESP-SA at various molar TESP-SA/MEL ratios (3/1, 2/1, 1/1). Subsequently, the cellulosic material was impregnated with the reaction mixtures and subjected to a thermal treatment at 160 °C and 220 °C. The physicomechanical data of the as-prepared cotton samples were evaluated. Various investigations have shown that the reaction of an amino functionality with vicinal carboxylic groups at elevated temperatures results in the formation of a cyclic imide group, which can be very well detected applying FT-IR spectroscopy (Ahmad et al. 2009; Clemson et al. 1997; Schramm and Rinderer 2015; Schramm et al. 2014).

The cotton samples are denoted as follow: RM: raw material; The first number indicates the molar ratio of TESP-SA/MEL (1 = 1/1, 2 = 2/1, 3 = 3/1), the second number refers to the amount of the impregnation steps, whereas the third number indicates the curing temperature (160 °C, 220 °C).

The physicomechanical data

Add-on

The cotton samples were impregnated once, twice or three times with the various treating solutions. Then the samples were dried and cured at elevated temperatures. The value of the add-on, which indicates the amount of the chemical agent being applied to the cotton sample, are listed in Table 1. A most significant increase can be observed when the molar ratio of TESP-SA/MEL is 2/1 and 3/1. The data make evident that the second impregnation step gives rise to an increase in the add-on values. The cotton samples which were treated at 220 °C exhibit a moderate increase in the add-on values compared to the samples having been cured at 160 °C.
Table 1

Physicomechanical properties of the cotton fabrics having been treated with various finishing baths containing TESP-SA and melamine

Code

Add-on (%)

Flexural rigidity (%)

Dry crease recovery angle (%)

Air permeability (%)

WI

Water retention (%)

Water vapor permeability (g/m2/48 h)

Crystallinity index (%)

RM

 

100.0

100.0

100.0

62.3

 

3091.0

71.9

1-1-160

6.55

276.4

156.9

127.2

51.3

28.9

2422.6

 

1-2-160

7.49

648.2

156.9

111.3

44.6

24.4

2488.8

71.3

1-1-220

10.47

1313.3

159.5

134.7

− 36.0

25.5

2320.9

 

1-2-220

9.17

1408.4

156.9

122.6

− 73.9

21.1

2317.7

69.7

2-1-160

9.49

453.9

156.9

131.0

44.9

25.9

2439.3

 

2-2-160

8.12

897.7

148.3

98.7

35.0

25.7

2326.1

72.3

2-1-220

15.84

1170.4

160.3

136.8

− 42.6

23.9

2476.6

 

2-2-220

14.79

1160.3

151.7

102.1

− 79.7

22.9

2545.0

68.2

3-1-160

9.45

1261.8

147.4

113.5

43.2

24.2

2563.7

 

3-2-160

7.57

1192.4

137.1

80.3

32.6

20.6

4005.7

72.7

3-1-220

16.66

2072.9

153.4

102.9

− 42.0

17.0

3928.6

 

3-2-220

16.68

2155.8

146.6

134.7

− 77.2

16.6

3901.2

66.2

Dry crease recovery angle

N-methylol compounds are the most commonly used cross-linking agents, which are very effective in conveying crease-resistant properties to cellulose-based material. Examples of these compounds include dimethylol urea (DMU), dimethylol ethylene urea (DMEU), trimethylol triazine (TMT), dimethylol methyl carbamate (DMMC), uron, triazone and the most effective dimethylol dihydroxy ethylene urea (DMDHEU). However, they suffer from various disadvantages, such as the tendency to release the irritant formaldehyde (Hewson 1994). Therefore, intensive efforts have been undertaken to replace DMDHEU.

Table 1 shows the DCRA values of the TESP-SA/MEL-treated cotton samples. Compared to the untreated fabric an improvement of the DCRA values can be observed. However, they do not reach the level of the commercial available durable press values.

Flexural rigidity

The bending properties of woven fabrics are of high interest for industrial, household and apparel applications (Chattopadhyay 2008; Ghosh et al. 1990). Therefore, the flexural rigidity values of the TESP-SA/MEL-treated cotton samples were measured. They are shown in Table 1 and make evident that an increase in the molar ratio of TESP-SA/MEL results in an enhancement of the flexural rigidity. The same tendency can be observed with respect to the number of impregnation steps. The highest value of flexural rigidity is obtained for 3-2-220.

Air permeability

The air permeability of a fabric is an indication of how well it enables the passage of air through it. The passage of air through a woven fabric is of importance for a number of fabric end uses such as industrial filters, tents, parachutes, raincoat materials, shirtings, and airbags (Morrissey and Rossi 2014; Ogulata 2006; Xiao et al. 2012).

The data of the measurement of the air permeability are shown in Table 1. The results make evident that no significant change can be observed, when the molar ratio was changed. A second impregnation step leads to a reduction of the air permeability indicating that the interstices in the cotton fabrics were reduced.

Whiteness index

When chemically modified cellulosic material is subjected to a thermal treatment various degradation processes of the cellulose and chemical agent may occur resulting in a reduction of the whiteness index. The WI values are presented in Table 1 and reveal that the curing process at 220 °C results in a significant reduction of the WI. This discoloration can mainly be ascribed to the reactions of carbonyl groups of the cellulosic material with the amino groups of melamine forming Schiff bases (De la Orden et al. 2004; De la Orden and Urreaga 2006).

Water retention

Due to the presence of hydroxyl groups in cellulosic materials, cotton is capable of taking up water. One portion of the water is bound to the surface and the other part remains between the fibers because of capillary actions. Therefore, the chemical modification of the cotton surface exerts an influence on the water retention value. The WRV are shown in Table 1 and make evident that an increase of the portion of melamine results in a moderate decrease of the water retention ability.

Water vapor permeability

The values of the water vapor permeability (WVP) which is governed by several structural and physicomechanical properties of the fabric are shown in Table 2 (Huang 2016). The data make evident that a significant increase of the WVP can be observed for those samples having been treated with finishing baths containing TESP-SA and MEL in the molar ratio 1:3.
Table 2

Whiteness indices of the bleached and TESP-SA/MEL modified cotton fabrics

Code

WI

Dry crease recovery angle

Untreated

Bleached

Untreated (%)

Bleached

Bath 1

Bath 2

Bath 1 (%)

Bath 2 (%)

RM

62.3

  

100.0

  

3-2-160

32.6

56.9

61.3

137.1

107.9

108.3

3-2-220

− 77.2

− 38.0

− 20.4

146.6

106.0

108.6

Morphology of the treated cotton fabrics

The SEM images of the cotton samples which have been impregnated once with TESP-SA/MEL solutions containing the components at different molar ratio (1/1, 1/2 and 1/3) are shown at two magnifications (500×, 3000×) in Fig. 2a–f (2a, b: 1-1-220, 2c, d: 2-1-220, 2d, f: 3-1-220). The SEM observations confirm that an obvious change in the surface morphology of the cotton fabrics can be seen after sol–gel coating. The typical longitudinal fibril structure of the native cotton disappears in all treated samples and the surface of fiber appears as a rough coating.
Fig. 2

The SEM images (two magnifications: 500×, 3000×) of the cotton samples which were impregnated once with TESP-SA/MEL solutions containing the components at different molar ratio (a, b: 1-1-220; c, d: 2-1-220; e, f: 3-1-220)

FT-IR spectra

FT-IR/ATR is an excellent tool to identify the functional group being present on the surface of cotton materials (Warren et al. 2016; Xue et al. 2016). Therefore, the spectra of the cotton samples which had been impregnated twice and which were treated at 160 °C and 220 °C have been recorded and are shown in Fig. 3. Figure 3a shows the spectrum of the untreated raw material. Figure 3b–d show the spectra of 1-2-160, 2-2-160 and 3-2-160. A peak can be observed at 1714 cm−1 which can be attributed to the stretching vibration of the carboxyl carbonyl bond present in TESP-SA. The amide I band (1631 cm−1) and the amide II band (1533 cm−1) prove the formation of a an amide functionality. The amide I band overlaps with the O–H bending mode of adsorbed water. The absorptions appearing in the spectral region of 1200 cm−1 to 800 cm−1 are assigned to the asymmetric vibration modes of the siloxane group and the asymmetric bridge C–O–C bonds of the cellulose. An inspection of the spectra of the cotton samples having been treated at 220 °C (Fig. 3e: 1-2-220, Fig. 3f: 2-2-220, Fig. 3g: 3-2-220) clearly make evident that an additional peak can be observed at 1784 cm−1. This absorption band indicates the formation of an imide group (imide I: asymmetric stretching mode of the carbonyl group). The corresponding symmetric vibrational mode can be seen at 1714 cm−1. The band at 1392 cm−1 is ascribed to the symmetric stretching vibration of the C–N group (imide II) (Schramm et al. 2014).
Fig. 3

FT-IR spectra of the raw material RM (a) and of the cotton samples which were impregnated twice with TESP-SA/MEL solutions containing the components at different molar ratio and which were treated at 160 °C: 1-2-160 (b), 2-2-160 (c) and 3-2-160 (d) and 220 °C: 1-2-220 (e), 2-2-220 (f) and 3-2-220 (g)

XRPD pattern

Cellulose comprises 1-4 linked β-d-glucose units and is known to exist in at least four polymorphic forms: cellulose I (native cellulose), cellulose II (regenerated cellulose and mercerized cellulose), cellulose III1, III11 (liquid ammonia treated cellulose), cellulose IV1, IV11 (thermally treated cellulose III) (O’Sullivan 1997). It is well known that cellulose is composed of crystalline regions (ordered) and amorphous regions (less ordered). Various methods have been used to evaluate the crystallinity of cellulose, such as FT-IR spectroscopy (Åkerholm et al. 2004; Warren et al. 2016) or X-ray powder diffraction (XRPD) (Ling et al. 2019; Park et al. 2010). In the present study XRPD was used to determine the CrI. The XRPD pattern of the treated cotton fabrics are shown in Fig. 4a–g. 4a: RM, 4b: 1-2-160, 4c: 1-2-160, 4d: 2-2-160, 4e: 2-2-220, 4f: 3-2-160, 4 g: 3-2-220). The XRD patterns with major peaks at 14.8, 16.4, 22.8 and 34.2, respectively which are assigned to the (1−10), (110), (200) and (004) diffraction planes indicate that cellulose I is present (Kim et al. 2018; Ling et al. 2019). The values of the CrI are shown in Table 1. The results reflect that the thermal treatment at 220 °C causes a reduction of the CrI values.
Fig. 4

XRPD pattern of the cotton samples which were impregnated twice and which were treated at 160 °C and 220 °C: RM (a), 1-2-160 (b), 1-2-220 (c), 2-2-160 (d), 2-2-220 (e), 3-2-160 (f) and 3-2-220 (g)

Mechanism of the crosslinking reaction

TESP-SA is hydrolyzed under acidic conditions. Consequently, the ethoxy groups which are attached to the silicon atom are converted into silanol groups and the anhydride moiety reacts to two carboxylic groups as shown in Fig. 5a. A nanosol solution is formed, which is added to a solution of melamine at elevated temperature. The carboxyl groups of the hydrolyzed TESP-SA react with the amino groups of melamine resulting in the formation of an amide functionality. This reaction mixture is applied to the cellulosic material. The thermal treatment at 220 °C results in the formation of the imide moiety (Fig. 5b).
Fig. 5

Reaction scheme of TESP-SA with melamine: hydrolysis of TESP-SA (a), reaction of hydrolyzed TESP-SA with melamine at a molar ratio of 3/1

The findings of the physicomechanical measurements make evident that an improvement of the DCRA values can be observed indicating that a crosslinking reaction was achieved. A tentative crosslinking scheme of the organic–inorganic hybrid with cellulose chains is shown in Fig. 6.
Fig. 6

Tentative crosslinking scheme of the organic–inorganic hybrid with cellulose chains

Bleaching of the cotton materials cured at 220 °C

As shown above, the curing process of TESP-SA/MEL-treated cotton samples at 220 °C results in a significant decrease in the WI value. Therefore, the cotton samples 3-2-160 and 3-2-220 were subjected to a bleaching process to improve the whiteness index. Two bleaching recipes were applied.

The findings which are presented in Table 2 make evident that the bleaching process gives rise to an increase in the WI. In the case of 3-2-160 the application of the bleaching bath containing 8% hydrogen peroxide causes a further improvement of the WI almost reaching the level of the raw material. The treatments of 3-2-220 with the bleaching baths give rise to an increase in the WI values. However, the level of the WI of the RM cannot be reached. Due to the alkaline conditions the values of the DCRA are significantly decreased.

Figure 7a–c show the FT-IR spectra of the raw material (7a), 3-2-220 (7b) and 3-2-220 having been treated with bleaching bath 2 (7c). The spectrum of 3-2-220 (Fig. 7b) shows the imide I bands (1782 c372 m−1 and 1708 cm−1) whose intensities are significantly reduced after the bleaching treatment (Fig. 7c). Figure 7c confirms that two new bands appear at 1556 cm−1 and at 1411 cm−1 which are ascribed to the asymmetric carbonyl stretching mode and the symmetric stretching mode of the carboxylate ion (COO) having been formed during the alkaline bleaching process (Chung et al. 2004; Oomens and Steill 2008).
Fig. 7

FT-IR spectra of the raw material (a), 3-2-220 (b) and 3-2-220 having been treated with bleaching bath 2 (c)

Conclusions

Cotton fabrics have been treated with an organic–inorganic hybrid based on the organotrialkoxysilane TESP-SA and with melamine in an attempt to convey crease-resistant properties to the cellulosic material. The hydrolyzed organotrialkoxysilane (3-triethoxysilylpropyl)succinic anhydride (TESP-SA) was reacted with 2,4,6-triamine-1,3,5-triazine (melamine) in an aqueous media at 160 °C and 220 °C. Three molar ratio TESP-SA/MEL were applied (1/1, 2/1, 3/1). The cotton fabrics were impregnated with the as-prepared solutions and thermally treated. An enhancement of the DCRA value could be observed. The thermal treatment at 220 °C gave rise to the formation of a polyimide group which was confirmed by means of FT-IR, however, the whiteness index was significantly reduced.

Notes

Acknowledgments

Open access funding provided by University of Innsbruck and Medical University of Innsbruck. The authors gratefully acknowledge the FFG (Österreichische Forschungsförderungs-gesellschaft) for financial support of the Project 846932 (Endowed Professorship in Advanced Manufacturing). The authors would like to thank the Testing Institute of the HTL Dornbirn (Austria) for making available textile-physical devices.

References

  1. Ahmad Z, Al Sagheer F, Al Arbash A, Ali AAM (2009) Synthesis and characterization of chemically cross-linked polyimide-siloxane hybrid films. J Non-Crystal Solids 355:507–517CrossRefGoogle Scholar
  2. Åkerholm M, Hinterstoisser B, Salmén L (2004) Characterization of the crystalline structure of cellulose using static and dynamic FT-IR spectroscopy. Carbohydr Res 339:569–578.  https://doi.org/10.1016/j.carres.2003.11.012 CrossRefGoogle Scholar
  3. Alongi J, Ciobanu M, Malucelli G (2011) Sol-gel treatments for enhancing flame retardancy and thermal stability of cotton fabrics: optimisation of the process and evaluation of the durability. Cellulose 18:167–177.  https://doi.org/10.1007/s10570-010-9470-2 CrossRefGoogle Scholar
  4. Arık B, Yavaş A, Avinc O (2017) Antibacterial and wrinkle resistance improvement of nettle biofibre using Chitosan and BTCA. Fibres Text East Eur 25:106–111.  https://doi.org/10.5604/01.3001.0010.1698 CrossRefGoogle Scholar
  5. Arık B, Avinc O, Yavas A (2018) Crease resistance improvement of hemp biofiber fabric via sol–gel and crosslinking methods. Cellulose 25:4841–4858.  https://doi.org/10.1007/s10570-018-1885-1 CrossRefGoogle Scholar
  6. Bajaj P (2002) Finishing of textile materials. J Appl Polym Sci 83:631–659.  https://doi.org/10.1002/app.2262 CrossRefGoogle Scholar
  7. Bann B, Miller SA (1958) Melamine and derivatives of melamine. Chem Rev 58:131–172.  https://doi.org/10.1021/cr50019a004 CrossRefGoogle Scholar
  8. Brinker CJ, Scherer GW (1990) Sol–gel science, the physics and chemistry of sol–gel processing. Academic Press, San DiegoGoogle Scholar
  9. Brzezinski S, Jasiorski M, Maruszewski K, Ornat M, Malinowska G, Borak B, Karbownik I (2007) Bacteriostatic textile-polymeric coat materials modified with nanoparticles. Polimery 52:362–366CrossRefGoogle Scholar
  10. Chattopadhyay R (2008) Design of apparel fabrics: role of fibre, yarn and fabric parameters on its functional attributes. J Text Eng 54:179–190.  https://doi.org/10.4188/jte.54.179 CrossRefGoogle Scholar
  11. Choi H-M, Kim JH, Shin S (1999) Characterization of cotton fabrics treated with glyoxal and glutaraldehyde. J Appl Polym Sci 73:2691–2699.  https://doi.org/10.1002/(sici)1097-4628(19990923)73:13%3c2691:Aid-app17%3e3.0.Co;2-t CrossRefGoogle Scholar
  12. Chung C, Lee M, Choe E (2004) Characterization of cotton fabric scouring by FT-IR ATR spectroscopy. Carbohydr Polym 58:417–420.  https://doi.org/10.1016/j.carbpol.2004.08.005 CrossRefGoogle Scholar
  13. Clemson PI, Pandiman D, Pearson JT (1997) Synthesis and characterization of new water-soluble precursors of polyimides. Polym Eng Sci 37:966–977CrossRefGoogle Scholar
  14. De la Orden MU, Urreaga JM (2006) Discoloration of celluloses treated with amino compounds. Polym Degrad Stab 91:886–893.  https://doi.org/10.1016/j.polymdegradstab.2005.06.022 CrossRefGoogle Scholar
  15. De la Orden MU, Matías MC, Martínez Urreaga J (2004) Discoloration of celluloses treated with polyethylenimines. Polym Degrad Stab 85:697–703.  https://doi.org/10.1016/j.polymdegradstab.2004.03.012 CrossRefGoogle Scholar
  16. Fink JK (2005) Reactive polymers: fundamentals and applications: a concise guide to industrial polymers. William Andrew Publishing Inc, New YorkGoogle Scholar
  17. French A, Santiago Cintrón M (2013) Cellulose polymorphy, crystallite size, and the Segal Crystallinity Index. Cellulose 20:583–588.  https://doi.org/10.1007/s10570-012-9833-y CrossRefGoogle Scholar
  18. Frick JG Jr, Harper RJ Jr (1984) Acetals as crosslinking reagents for cotton. J Appl Polym Sci 29:1433–1447.  https://doi.org/10.1002/app.1984.070290436 CrossRefGoogle Scholar
  19. Gambichler T, Avermaete A, Bader A, Altmeyer P, Hoffmann K (2001) Ultraviolet protection by summer textiles. Ultraviolet transmission measurements verified by determination of the minimal erythema dose with solar-simulated radiation. Br J Dermatol 144:484–489CrossRefGoogle Scholar
  20. Ghosh TK, Batra SK, Barker RL (1990) The bending behaviour of plain-woven fabrics part I: a critical review. J Text Inst 81:245–254CrossRefGoogle Scholar
  21. Harifi T, Montazer M (2012) Past, present and future prospects of cotton cross-linking: new insight into nano particles. Carbohydr Polym 88:1125–1140.  https://doi.org/10.1016/j.carbpol.2012.02.017 CrossRefGoogle Scholar
  22. Hearle JW (2002) Fibers, 2. Structure. Wiley-VCH, WeinheimGoogle Scholar
  23. Hench LL, West JK (1990) The sol–gel process. Chem Rev 90:33–72CrossRefGoogle Scholar
  24. Hewson M (1994) Formaldehyde in textiles. J Soc Dyers Colour 110:140–142CrossRefGoogle Scholar
  25. Hobart SR, Mack CH (1969) Reaction of aryl isocyanates with cotton cellulose: part V: Reaction via diphenyl N, N′-arylenedicarbamates. Text Res J 39:317–323.  https://doi.org/10.1177/004051756903900402 CrossRefGoogle Scholar
  26. Huang J (2016) Review of heat and water vapor transfer through multilayer fabrics. Text Res J 86:325–336.  https://doi.org/10.1177/0040517515588269 CrossRefGoogle Scholar
  27. Huang KS, Hwang MC, Chen JS, Lin SJ, Wang SP (2007) Application of mixed gel solution in the anti-wrinkle finishing of cotton fabrics. J Text Inst 98:169–176.  https://doi.org/10.1533/joti.2005.0300 CrossRefGoogle Scholar
  28. Ju X, Bowden M, Brown EE, Zhang X (2015) An improved X-ray diffraction method for cellulose crystallinity measurement. Carbohydr Polym 123:476–481.  https://doi.org/10.1016/j.carbpol.2014.12.071 CrossRefGoogle Scholar
  29. Katovic D, Flinčec Grgac S, Bischof-Vukušić S, Katović A (2012) Formaldehyde free binding system for flame retardant finishing of cotton fabrics fibres. Text East Eur 20:94–98Google Scholar
  30. Kim HJ, Liu Y, French AD, Lee CM, Kim SHJC (2018) Comparison and validation of Fourier transform infrared spectroscopic methods for monitoring secondary cell wall cellulose from cotton fibers. Cellulose 25:49–64.  https://doi.org/10.1007/s10570-017-1547-8 CrossRefGoogle Scholar
  31. Kottes Andrews BA, Trask-Morell BJ (1996) Long term formaldehyde emissions from DMDHEU-finsihed cotton fabrics. Text Chem Color 29:16–19Google Scholar
  32. Lam YL, Kan CW, Yuen CW (2011a) Wrinkle-resistant finishing with dimethyloldihydroxyethyleneurea (DMDHEU)—the effect of co-catalyst. Text Res J 81:1419–1426.  https://doi.org/10.1177/0040517510387206 CrossRefGoogle Scholar
  33. Lam YL, Kan CW, Yuen CWM (2011b) Effect of titanium dioxide on the flame-retardant finishing of cotton fabric. J Appl Polym Sci 121:267–278.  https://doi.org/10.1002/app.33618 CrossRefGoogle Scholar
  34. Ling Z et al (2019) Effects of ball milling on the structure of cotton cellulose. Cellulose 26:305–328.  https://doi.org/10.1007/s10570-018-02230-x CrossRefGoogle Scholar
  35. Mahbubul Bashar M, Khan M (2013) An overview on surface modification of cotton fiber for apparel use. J Polym Environ 21:181–190.  https://doi.org/10.1007/s10924-012-0476-8 CrossRefGoogle Scholar
  36. Mahltig B, Textor T (2008) Nanosols and textiles. World Scientifics, LondonCrossRefGoogle Scholar
  37. Montazer M, Afjeh MG (2007) Simultaneous X-linking and antimicrobial finishing of cotton fabric. J Appl Polym Sci 103:178–185.  https://doi.org/10.1002/app.25059 CrossRefGoogle Scholar
  38. Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40:3941–3994.  https://doi.org/10.1039/c0cs00108b CrossRefGoogle Scholar
  39. Morrissey MP, Rossi RM (2014) The effect of wind, body movement and garment adjustments on the effective thermal resistance of clothing with low and high air permeability insulation. Text Res J 84:583–592.  https://doi.org/10.1177/0040517513499431 CrossRefGoogle Scholar
  40. Muresan EI, Balan G, Popescu V (2013) Durable hydrophobic treatment of cotton fabrics with glycidyl stearate. Ind Eng Chem Res 52:6270–6276.  https://doi.org/10.1021/ie400235u CrossRefGoogle Scholar
  41. Ogulata RT (2006) Air permeability of woven fabrics. J Text Appar Technol Manag 5:1–10Google Scholar
  42. Oomens J, Steill JD (2008) Free carboxylate stretching modes. J Phys Chem A Lett 112:3281–3283Google Scholar
  43. O’Sullivan A (1997) Cellulose: the structure slowly unravels. Cellulose 4:173–207.  https://doi.org/10.1023/a:1018431705579 CrossRefGoogle Scholar
  44. Park S, Baker JO, Himmel ME, Parilla PA, Johnson DK (2010) Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance. Biotechnol Biofuels 3:10.  https://doi.org/10.1186/1754-6834-3-10 CrossRefGoogle Scholar
  45. Paul R (2015) Functional finishes for textiles: an overview. In: Paul R (ed) Functional finishes for textiles. Woodhead Publishing, Cambridge, pp 1–14.  https://doi.org/10.1533/9780857098450.1 Google Scholar
  46. Pinho E, Soares G (2018) Functionalization of cotton cellulose for improved wound healing. J Mater Chem B 6:1887–1898.  https://doi.org/10.1039/C8TB00052B CrossRefGoogle Scholar
  47. Pipatchanchai T, Srikulkit K (2007) Hydrophobicity modification of woven cotton fabric by hydrophobic fumed silica coating. J Sol-Gel Sci Technol 44:119–123CrossRefGoogle Scholar
  48. Reinhardt RM, Kullman RMH, Moore HB, Reid JD (1961) The use of coreactant curing agents with a diepoxide to impart wrinkle resistance to cotton fabrics. Text Res J 31:941–950.  https://doi.org/10.1177/004051756103101104 CrossRefGoogle Scholar
  49. Rowland SP, Brannan MAF (1970) Introduction and removal of durable creases in wrinkle-resistant cotton fabric. Text Res J 40:607–613.  https://doi.org/10.1177/004051757004000705 CrossRefGoogle Scholar
  50. Roy D, Semsarilar M, Guthrie JT, Perrier S (2009) Cellulose modification by polymer grafting: a review. Chem Soc Rev 38:2046–2064.  https://doi.org/10.1039/B808639G CrossRefGoogle Scholar
  51. Schramm C, Rinderer B (2006) Application of polycarboxylic acids to cotton fabrics under mild curing conditions. Cellul Chem Technol 40:799–804Google Scholar
  52. Schramm C, Rinderer B (2015) Non-formaldehyde, crease-resistant modification of cellulosic material by means of an organotrialkoxysilane and metal alkoxides. Cellulose 22:2811–2824.  https://doi.org/10.1007/s10570-015-0664-5 CrossRefGoogle Scholar
  53. Schramm C, Rinderer B (2017) Modification of cotton fabrics with a hydrolysed organotrialkoxysilane/metal alkoxide system: multifunctionalisation and mordant dyeing. Color Technol 133:234–242.  https://doi.org/10.1111/cote.12274 CrossRefGoogle Scholar
  54. Schramm C, Binder W, Tessadri R (2004) Durable press finishing of cotton fabric with 1,2,3,4-butanetetracarboxylic acid and TEOS/GPTMS. J Sol-Gel Sci Technol 29:155–165CrossRefGoogle Scholar
  55. Schramm C, Binder WH, Tessadri R, Duelli H (2005) Modification of cotton fabrics by means of hydrolyzed TEOS-, GPTMS- and Ti(OiPr)3(acac)-solutions. Cellul Chem Technol 39:303–314Google Scholar
  56. Schramm C, Rinderer B, Tessadri R (2014) Non-formaldehyde, crease resistant agent for cotton fabrics based on an organic–inorganic hybrid material. Carbohydr Polym 105:81–89.  https://doi.org/10.1016/j.carbpol.2014.01.063 CrossRefGoogle Scholar
  57. Steele R (1961) The reactivity of some epoxides toward cellulose. Text Res J 31:257–262.  https://doi.org/10.1177/004051756103100303 CrossRefGoogle Scholar
  58. Tesoro GC, Linden P, Sello SB (1961) Chemical modification of cotton with derivatives of divinyl sulfone. Text Res J 31:283–295.  https://doi.org/10.1177/004051756103100401 CrossRefGoogle Scholar
  59. Tomasino C, Wilson TW, Goynes RR (1982) Urethane prepolymers as durable press finishes. Ind Eng Chem Prod Res Dev 21:4–11CrossRefGoogle Scholar
  60. Trask-Morell BJ, Kottes Andrews BA, Vinyard BJ (1996) Thermoanalytical study of durable press reactant levels on cotton fabrics part II finshes based on DMDHEU. Text Res J 99:172–183CrossRefGoogle Scholar
  61. Vail SL, Arney WC (1971) Reaction mechanisms of glyoxal-based durable-press resins with cotton. Text Res J 41:336–344.  https://doi.org/10.1177/004051757104100410 CrossRefGoogle Scholar
  62. Wang L, Zhang X, Li B, Sun P, Yang J, Xu H, Liu Y (2011) Superhydrophobic and ultraviolet-blocking cotton textiles. ACS Appl Mater Interfaces 3:1277–1281.  https://doi.org/10.1021/am200083z CrossRefGoogle Scholar
  63. Warren FJ, Gidley MJ, Flanagan BM (2016) Infrared spectroscopy as a tool to characterise starch ordered structure—a joint FTIR-ATR, NMR, XRD and DSC study. Carbohydr Polym 139:35–42.  https://doi.org/10.1016/j.carbpol.2015.11.066 CrossRefGoogle Scholar
  64. Welch CM (1994) Formaldehyde-free DP finishing with polycarboxylic acids. Am Dyestuff Rep 83:19–36Google Scholar
  65. Welch CM, Andrews BK (1989) Catalysts and processes for formaldehyde-free durable press finishing of cotton textiles with polycarboxylic acids. WO8912714A1Google Scholar
  66. Wright JD, Sommerdijk NAJM (2001) Sol–gel materials chemistry and applications. Gordon and Breach Science Publisher, AmsterdamGoogle Scholar
  67. Xiao X, Zeng X, Bandara P, Long A (2012) Experimental study of dynamic air permeability for woven fabrics. Text Res J 82:920–930.  https://doi.org/10.1177/0040517511429605 CrossRefGoogle Scholar
  68. Xue Y, Patel A, Sant V, Sant S (2016) Semiquantitative FTIR analysis of the crosslinking density of poly(ester amide)-based thermoset elastomers. Macromol Mater Eng 301:296–305.  https://doi.org/10.1002/mame.201500190 CrossRefGoogle Scholar
  69. Yamamoto K (1982) Crease-resistance finishing of cotton fabrics with acrylate copolymers and DMDHEU. Text Res J 52:363–369CrossRefGoogle Scholar
  70. Yang CQ, Wang XL (1998) Applications of FT-IR spectroscopy to the studies of esterification and crosslinking of cellulose by polycarboxylic acids: part I. Formation of cyclic anhydrides as the reactive intermediates. In: deHaseth JA (ed) Fourier transform spectroscopy. AIP conference proceedings, vol 430, pp 661–664.  https://doi.org/10.1063/1.55748
  71. Yeqiu L, Jinlian H, Yong Z, Zhuohong Y (2005) Surface modification of cotton fabric by grafting of polyurethane. Carbohydr Polym 61:276–280.  https://doi.org/10.1016/j.carbpol.2005.03.010 CrossRefGoogle Scholar
  72. Zhang M, Wang C (2013) Fabrication of cotton fabric with superhydrophobicity and flame retardancy. Carbohydr Polym 96:396–402.  https://doi.org/10.1016/j.carbpol.2013.04.025 CrossRefGoogle Scholar
  73. Zheng CH, Chen GQ, Qi ZM (2011) Ultraviolet resistant/antiwrinkle finishing of cotton fabrics by sol-gel method. J Appl Polym Sci 122:2090–2098.  https://doi.org/10.1002/app.34289 CrossRefGoogle Scholar

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Authors and Affiliations

  1. 1.Research Institute of Textile Chemistry and Textile PhysicsUniversity InnsbruckDornbirnAustria

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