Wear Properties of Hemp, Ramie and Linen Fabrics After Liquid Ammonia/Crosslinking Treatment

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Jun Li, Jiahao Feng, Wear Properties of Hemp, Ramie and Linen *Hua Zhang, *Jianchun Zhang Fabrics after Liquid Ammonia/Crosslinking Treatment

Key Laboratory of Clothing, Design & Technology, Abstract Ministry of Education, Desized and scoured hemp, ramie and linen fabrics were treated with liquid ammonia over Fashion Institute, practical ranges, followed by crosslink finishing with modified DMDHEU (Clariant Chemical Co). Appearance qualities, as well as comfort and mechanical properties were measured to in- *College of Textiles, Donghua University, vestigate the wear behavior of all-cellulosic fabrics. The crease recovery, washing shrinkage and Shanghai, China other appearance qualities of cellulosic fabrics were improved by NH3 treatment and especially E-mail: [email protected] by liquid ammonia pretreatment in conjunction with crosslink finishing. The moisture regain of the cellulosic fibers was increased by NH3 treatment, but on the other hand, water retention was decreased. The air permeability, moisture permeability and other comfort properties of the cellulosic fabrics were decreased by crosslink finishing, whereas those of NH3/crosslinked fabrics were greater than untreated ones. As a pretreatment for crosslink finishing, liquid ammonia significantly improved the tensile strength retention and tear strength in cellulosic fabrics compared to crosslink finishing alone. Key words: liquid ammonia treatment, crosslink treatment, hemp, ramie, linen, fabrics, wear properties.

lulosic fabrics. However, for such fabric which residual ammonia was removed by properties as shape retention and mainte- hot water. The fabrics remained taut in nance, it is difficult to satisfy consumers the warp because of the continuous oper- by NH3 treatment alone [2 - 6]. With the ation but were not stretched in the filling introduction of all-cotton no-iron shirts direction. Resin treatment was performed to the consumer market, there is renewed in a pilot plant as a continuous operation. interest in treatments that will provide An Arkofix NETM (modified DMD- the consumer with the comfort of cotton, HEU) resin (60 g/L) was applied by the the convenience and appearance of dura- conventional pad-dry-cure process using ble press, and adequate wear behaviour. catalysts NKC (18 g/L), protective agent The use of liquid ammonia treatment in HDP (High Density Polyethlene 15 g/L) conjunction with resin finish has become one focus because it not only improves and silicone fabric softeners UP (Unsatu- appearance qualities but also provides rated Polyester 25 g/L). All reagents used high strength retention to all-cellulosic in the resin treatment were provided by fabrics [7 - 11]. the Clariant Chemical Co., Ltd.

In this study, the modifying effects of Measurements liquid ammonia treatment alone and in Crease recovery was measured with a conjunction with resin treatment on ap- crease recovery angle tester according to pearance qualities as well as comfort and the ISO 2313-1972 method in both the mechanical properties are discussed. warp and filling directions. The sample n Introduction was washed three times in a domestic Parallel to the development of the pro- n Experimental electric washing machine according to grade process for the liquid ammonia the AATCC-135 test method. treatment of yarns was the development Experimental materials of a process for the liquid ammonia treat- Desized and scoured hemp as well as Bending rigidity was measured accord- ment of fabrics by the Norwegian Textile ramie and linen fabrics (Table 1) were ing to the bevel method. Then the can- Research. This work was begun in 1963, treated with liquid ammonia in mass tilever bending stiffness B and bending and the necessary machinery was com- manufacturing conditions (Youngor Sun- modulus q were calculated by the follow- pleted in mid-1970 [1]. Liquid ammonia rise Textile D & F Co., Ltd, China). The ing equations [12]: treatment imparts wrinkle recovery, soft fabrics were saturated with NH3 for 2 handle and mechanical properties to cel- seconds and dried on steam cans, during B = G×(0.5L)3×10-1 in mg·cm (1)

Table 1. Details of experimental materials. Experimental Yarn constitution Weave Yarn linear density, Surface mass, Warp density, Weft density, materials (warp, weft) construction tex (warp,weft) g/m2 per 10cm per 10 cm Hemp fabric 100% Hemp, 100% Hemp Plain 72, 72 183 212 212 Ramie fabric 100% Ramie, 100% Ramie Plain 72, 72 178 212 212 Linen fabric 100% Linen, 100% Linen Plain 72, 72 167 228 197

Li Jun, Feng Jiahao, Zhang Hua, Zhang Jianchun; Wear Properties of Hemp, Ramie and Linen Fabrics after Liquid Ammonia/Crosslinking Treatment. 81 FIBRES & TEXTILES in Eastern Europe 2010, Vol. 18, No. 5 (82) pp. 81-85. resin finishing agent and allows the dif- 300 Hemp Ramie Linen fusion of the cross-linker into the interior Hemp Ramie Linen 2 Dry of the fibers.Figure 1 also shows that the 250 Wet 0 wet crease recovery of cellulosic fabrics 200 is greater than that of the same sample -2

in dry conditions, indicating that hemp, 150 -4 ramie and linen fabrics have better appearance retention in wet conditions. 100 shrinkage, % Washing Washing shrinkage (%) shrinkage Washing -6 crease recovery angle (degree) angle recovery crease Crease recovery angle, degree 50 -8 a b c d a b c d a b c d Figure 2 shows that resin treated fab- Warp Filling rics have good dimensional stability compared to non-resin treated fabrics. Figure 1. Crease recovery angles of (a) Figure 2. Washing shrinkage of (a) untre- Crosslinked fabrics show a less than 4% untreated, (b) NH3 treated, (c) crosslinked, ated, (b) NH3 treated, (c) crosslinked, and shrinkage in the warp and a less than 1% and (d) NH /crosslinked fabrics. (d) NH /crosslinked fabrics. 3 3 shrinkage in the filling direction. The untreated hemp and linen fabrics have around 7% shrinkage in the warp direc-

1000 240 tion and 5% shrinkage in the filling di- Hemp Ramie Linen ) 900 Hemp Ramie Linen -2 cm · 800 ) 200 rection, while the NH3 treated hemp and cm . mg

( 700

cm linen fabrics have around 5.5% washing . kg/cm2 160 600 ( shrinkage in the warp and 1% extensibil- 500 120

400 ity in the filling directions. The fabrics 300 80 were held taut in the warp direction dur- stiffness, mg stiffness, Cantilever bending 200 Bending modulus Bending 40 ing the finishing operations but were not 100 Bending modulus, kg Cantilever bending stiffness bending Cantilever 0 0 stretched in the filling direction, which a b c d a b c d is reflected in their shrinkage behaviour. As stresses were relieved in laundering, Figure 3. Cantilever bending stiffness of Figure 4. Bending modulus of (a) untre- the warp yarns held taut in the finishing (a) untreated, (b) NH3 treated, (c) crosslin- ated, (b) NH3 treated, (c) crosslinked, and operation had greater shrinkage. As for ked, and (d) NH3/crosslinked fabrics. (d) NH3/crosslinked fabrics. washing shrinkage, however, after liquid ammonia treatment, ramie fabric is dif- where G is fabric weight per unit area in water retention were obtained [13, 14]. ferent from hemp and linen fabrics. g/m2 and L is fabric slip length in cm Air permeability was measured according to the ISO 9237-1995 test method. q = 12B/t3 × 10-3 in kg/cm2 (2) Figure 3 shows the cantilever bending Moisture permeability was measured stiffness of hemp, ramie and linen fabrics by the evaporation method [15]. Tear where t is fabric thickness in mm. resulting from NH3 and resin treatments. strength was assessed according to the The cantilever bending stiffness of hemp, The fabrics were immersed in water, then ASTM D2261 test method. The breaking ramie and linen fabrics is increased by centrifuged and dried. Moisture regain and load and extensibility were assessed ac- liquid ammonia treatment, whereas it cording to the ASTM D5035 test method. is decreased by resin treatment because Table 2. Crystallinity of hemp, ramie and of softeners in the finishing agent. The linen fibers. n Results and discussion bending modulus reflects fiber rigidity, which is not affected by fabric thick- Treatment Hemp Ramie Linen Appearance qualities ness. The bending modulus is decreased Control 84.79 84.48 80.33 Figure 1 shows that liquid ammonia by NH3 treatment, except for ramie fab- NH - treatment increases wrinkle recovery ric, as shown in Figure 4. For example, 3 72.84 76.43 75.86 treated in the fabrics. The loss of moderate the bending modulus of untreated hemp to large pores is therefore associated and linen is 175.5 and 163.63 kgf/cm2, after liquid ammonia treatment - with increased resilience. These pores 12 are voids between elementary fibres or 157.10 and 128.05 kgf/cm2, and that of Hemp Ramie Linen 10 microfibrils, and their loss affects the NH3/crosslinked fabrics is 112.5 and closer lateral association between micro- 115.94 kgf/cm2, respectively. However, 8 fibrillar units, which is a natural sort of the bending modulus of untreated ramie is 6 2 2 crosslinking via lateral hydrogen bond- 121.01 kgf/cm , reaching 130.32 kgf/cm after NH treatment and 126.93 kgf/cm2 4 ing. The crease recovery angles of cel- 3 Moisture regain, % lulosic fabrics are considerably increased after NH3/crosslinked treatment. Moisture regain (%) regain Moisture 2 by crosslink finishing and especially by 0 Comfort properties a b c d NH3/crosslink finishing. With the increased amorphous region for larger ac- Liquid ammonia treatment not only re- cessible internal volume, liquid ammonia sults in a larger proportion of amorphous Figure 5. Moisture regain of (a) untreated, pretreatment increases the number of regions but also disorders parts of the (b) NH3 treated, (c) crosslinked, and (d) NH3/crosslinked fabrics. crosslinked bonds between the fibers and crystallite region, as shown in Table 2;

82 FIBRES & TEXTILES in Eastern Europe 2010, Vol. 18, No. 5 (82) a) b) c) d)

Figure 6. Surface SEM photograph of untreated hemp, ramie and linen fibers; a) Hemp (×2 000), b) Linen (×2 000), c) Ramie (×2 000), Ramie (×5 000).

a) b) c) d)

Figure 7. Surface SEM photograph of NH3 treated hemp, ramie and linen fibers; a) Hemp (×2 000), b) Linen (×2 000), c) Hemp (×5 000), d) Ramie (×2 000).

80 1050 Hemp Ramie Linen 80

70 s) .

2 Hemp Ramie Linen Hemp Ramie Linen 900 70 60 /(m 3 60 750 50 50 40 600

30 450 30

Water retention, % Water 20 300

Water retention (%) retention Water 20 Moisture permeability, % Moisture permeability, 10 ) (L/m2.s permeability Air 150 Moisture permeability (%) permeability Moisture

Air permeabilityd, dcm 10

0 0 0 a b c d a b c d a b c d

Figure 8. Water retention of (a) untreated, Figure 9. Air permeability of (a) untreated, Figure 10. Moisture permeability of (a) (b) NH3 treated, (c) crosslinked, and (d) (b) NH3 treated, (c) crosslinked, and (d) untreated, (b) NH3 treated,(c) crosslinked, NH3/crosslinked fabrics. NH3/crosslinked fabrics. and (d) NH3/crosslinked fabrics fibers. hence the moisture regain of hemp, ramie Figure 6 also shows that there are many ity of cellulosic fabrics is considerably and linen fabrics is increased by NH3 bigger ravines on ramie fibers, making it improved by NH3 treatment, especially treatment, as shown in Figure 5. The easier to absorb water from its particular hemp fabric. The yarns of cellulisic fab- moisture regain of cellulosic fabrics is approaches. After liquid ammonia treat- rics became fleecy after swelling treat- decreased by crosslink finishing, whereas ment the water retention of hemp and ment and subsequent hot water process- that of NH3/crosslinked fabrics is greater linen fabrics is considerably higher than ing. The reduction in crevices on the fiber than untreated ones. that of ramie fabrics, as shown in Fig- surface resulted in increased changes ure 8, resulting in a decrease in the space with respect to ventilation. The moisture As compared to ramie fiber, hemp and for holding water. Hence the water reten- permeability of hemp, ramie and linen linen fibers are slender, and many of tion of cellulosic fabrics is decreased by fabrics is improved by the swelling fin- which are oblate. In the same character- NH3 treatment, especially for hemp and ish, as shown in Figure 10, the reason istic fabric conditions, there are many linen fabrics. This behaviour is almost for which is almost the same as for air more soakage spaces in hemp and linen the same as that with the NH3 treatment permeability in the NH3 treatment of fabrics than in ramie, which is required of cotton [13, 14]. For deposited resin in cellulosic fabrics. The air and moisture for the water retention of all-cellulosic the pores of fibers and on their surfaces, permeability of cellulosic fabrics are de- fabrics. What is more, there are many the water retention of crosslinked fab- creased by resin treatment, whereas that striations, crevices and narrower ra- rics became lower, especially cellulosic of NH3/crosslinked fabrics is still greater vines on the surface of hemp and linen fabrics after liquid ammonia pretreat- than untreated ones. fibers, whereas there are few or none ment and in conjunction with crosslink on the surface of ramie fiber, as shown finishing. Mechanical properties in Figure 6. The number of crevices de- Figure 11 shows the strength at rupture creased greatly and the surface of fibers Figure 9 shows the air permeability of of hemp, ramie and linen fabrics after became much smoother after liquid am- hemp, ramie and linen fabrics after NH3 NH3 and resin treatments. The strength monia treatment, as shown in Figure 7. and resin treatments. The air permeabil- in the warp of cellulosic fabrics is im-

FIBRES & TEXTILES in Eastern Europe 2010, Vol. 18, No. 5 (82) 83 cellulosic fabrics could be improved by 50 liquid ammonia pretreatment and in con- Hemp Ramie Linen 1800 45 Warp Untreated Ramie Filling 40 Treated Ramie junction with resin treatment. 1500 35

30 1200 25

n 20 Conclusions 900 15 The crease recovery, washing shrinkage, Strength at rupture (N) rupture at Strength 600 10 5 bending modulus and other appearance Differential accessible volume V.lb(ml/g) volume accessible Differential 300 0 a b c d 0 20 40 60 80 100 120 140 160 qualities of hemp, ramie and line fabrics Diameter of micpores D(A) are improved by NH3 treatment, especially by liquid ammonia pretreatment Figure 11. Strength at rupture of (a) untre- Figure 12. Relationship between the diffe- and in conjunction with crosslink finish- ated, (b) NH3 treated,(c) crosslinked, and rential accessible volume and diameters of (d) NH3/crosslinked fabrics crosslinked. micpores in ramie fiber. ing.

The moisture regain, air permeability and 60 64 Hemp Ramie Linen moisture permeability of cellulosic fab- Hemp Ramie Linen 56 Warp 50 Warp Filling rics are all increased by liquid ammonia Filling 48 treatment, whereas they are decreased by 40 40 crosslink finishing; and those of3 NH / 30

32 crosslinked cellulosic fabrics are greater 20 than untreated ones. 24 Tearing strength (N) strength Tearing

Elongation at rupture (%) rupture at Elongation 10 16 The water retention of hemp, ramie and 0 8 a b c d a b c d linen fabrics is decreased by NH3 treatment, especially by liquid ammonia Figure 13. Elongation at rupture of (a) Figure 14. Tear strength of (a) untreated, pretreatment and subsequent crosslink untreated, (b) NH3 treated, (c) crosslinked, (b) NH3 treated, (c) crosslinked, and (d) finishing. and (d) NH3/crosslinked fabrics. NH3/crosslinked fabrics. The strength of hemp, ramie and linen fabrics is increased by liquid ammonia proved, whereas in the filling direction fibers more uniform after NH3 treatment. it is decreased by the liquid ammonia The distribution of resin and crosslink- treatment with load application. NH3/ treatment. The fabrics were held taut in ing bonds becomes uniform, leading to crosslinked cellulosic fabrics have higher the warp direction during the finishing improved mechanical properties of cel- strength retention in the warp and filling operations but were not stretched in the lulosic fabrics. directions, as compared to fabrics after filling direction. According to Koichi crosslink finishing alone. Goda and et al [16], it can be concluded Figure 13 shows the elongation at rup- that microfibrils with a load application ture of hemp, ramie and linen fabrics The tear strength of hemp and linen fab- during liquid ammonia treatment become after NH3 and resin treatments. Extensi- rics is increased after crosslink finishing, more oriented along the axis of tension, bilities in the warp of cellulosic fabrics while that of ramie is decreased. In gen- as compared to microfibrils without load are decreased a little by NH3 treatment, eral, the tear strength of NH3/crosslinked application. After crosslink finishing, the however, they are considerably increased hemp, ramie and linen fabrics is greater strength of crosslinked cellulosic fabrics in the filling direction, which is attributed than corresponding untreated ones. is considerably decreased. However, to the fabrics being held taut in the warp NH3/crosslinked cellulosic fabrics have direction and not stretched in the filling higher strength retention in the warp and direction during liquid ammonia treat- References filling directions, as compared to fabrics ment. The elongation at rupture in the 1. Stevens C, and Roldan L G., Liquid am- after crosslink finishing alone. two directions of hemp, ramie and linen monia treatment of textiles, Handbook of fabrics undergoes no big changes during fiber science and technology, Chemical Processing of Fibers and Fabrics, Fun- Firstly, the strength in the warp of hemp, resin treatment. damentals and Preparation Part A, Vol. ramie and linen fabrics is increased by 1 (1983) pp. 170-176. liquid ammonia treatment, as shown in Figure 14 shows the tear strength of 2. Wakida T., Kida Y., Lee M., Bae S., Figure 11. Secondly, the volume of mi- hemp, ramie and linen fabrics after NH3 Yoshioka H., Yanai Y.; Dyeing and Me- cropores with a diameter larger than 36Å and resin treatments. The changes in chanical Properties of Cotton Fabrics is decreased by liquid ammonia treat- hemp, ramie and linen fabrics are dif- Treated with Sodium Hysroxide/Liquid ment, while that of micropores smaller ferent in the warp and filling directions Ammonia/Sodium Hysroxide, Textile Res. J. 70 (2000) pp. 328-332. than 36Å is increased, as shown in after NH3 treatment. The tear strength of Figure 12 [17]. Liquid ammonia treat- hemp and linen fabrics is increased after 3. Wakida T., Hayashi A., Lee M. S., Lee M., Doi C., Okada S., Yanai Y.; Dyeing ment increases the volume of smaller crosslink finishing, while that of ramie and Mechanical Properties of Ramie Fa- micropores and decreases that of larger fabric is decreased. In general, the tear bric Treated with Liquid Ammonia, Sen’I ones in ramie fiber. As a result, the size strengths of NH3/crosslinked cellulosic Gakkaishi 57 (2001) pp. 148-152. distribution of cellulosic fiber becomes fabrics are all greater than the crosslinked 4. Lee M., Wakida T., Tokuyama T., Doi C., narrow and micropore distribution in the ones, indicating that the tear strength of Lim Y. J., Jeon S.; Liquid Ammonia Treat-

84 FIBRES & TEXTILES in Eastern Europe 2010, Vol. 18, No. 5 (82) ment of Regenerated Cellulosic Fabrics, Textile Res .J. 75 (2005) pp. 13-18. 5. Wakida T., Kitamura Y., Lee M., Bae S., INSTITUTE OF BIOPOLYMERS Chen, M., Yoshioka H., Yanai Y.; Effect of AND CHEMICAL FIBRES Hot Water Processing on Dyeing and Me- chanical Properties of Cotton Treated with Liquid Ammonia and Sodium Hydroxide, LABORATORY OF PAPER QUALITY Textile Res. J. 70 (2000) pp. 769-774. 6. Wakida T., Hayashi A., Lee M.S., Lee M., Okada S., Yanai Y., Liquid Ammonia Treatment of Lyocell, Sen’I Gakkaishi 57 Since 02.07.1996 the Laboratory has had the accreditation (2001) pp. 355-358. certificate of the Polish Centre for Accreditation 7. Raheel M., Lien M. D.; Modifying wear life No AB 065. of all-cotton fabrics. Part I: Liquid ammonia treatment and durable press finish, The accreditation includes tests of more than 70 proper- Textile Res. J. 70 (1982) pp. 493-503. ties and factors carried out for: 388 n 8. Wakida T., Hayashi A., Saito M., Lee M. pulps S., Lee M., Okada, S., Yanai Y.; Liquid n tissue, paper & board, Ammonia Treatment of Polyester/Cotton n cores, Fabric, Sen’I Gakkaishi 57 (2001) pp. n transport packaging, 60-63. n auxiliary agents, waste, wastewater and process water in the pulp and 9. Heap S. A.; Liquid ammonia treatment of paper industry. cotton fabrics as a pretreatment for easy- care finishing, Textile Inst. Ind. 6 (1978) The Laboratory offers services within the scope of testing the following: pp. 387-390. raw ‑materials, intermediate and final paper products, as well as training 10. Jung H.; Liquid ammonia vs caustic mer- activities. cerization as a pretreatment for the cotton butadienediepoxide reaction, spectra and microscopic studies, Textile Res. J. 45, Properties tested: (1975) pp. 681-691. n general (dimensions, squareness, grammage, thickness, fibre furnish 11. Vail S. L., Verburg G. B , Calamari T. A.; analysis, etc.), Ammonia mercerization improves tensile n chemical (pH, ash content, formaldehyde, metals, kappa number, etc.), properties of durable-press cotton cham- n surface (smoothness, roughness, degree of dusting, sizing and picking of bray, Textile Chem. Color. 7 (1975) pp. a surface), 26-27. n absorption, permeability (air permeability, grease permeability, water 12. GUO Ya-lin; Research on the dyeing absorption, oil absorption) and deformation, properties of flax with chemical modified, n Tianjing University, (2001) pp. 59-60. optical (brightness ISO, whitness CIE, opacity, colour), 13. Yuichi Yanai, Kunihiro Hamada, Yoshio n tensile, bursting, tearing, and bending strength, etc., Shimizu; The liquid ammonia treatment n compression strength of corrugated containers, vertical impact testing by of cotton fibers-Comparison and combi- dropping, horizontal impact testing, vibration testing, testing corrugated nation with mercerization using a practical containers for signs „B” and „UN”. unit, Sen’i Gakkaishi, Vol. 62, No. 4, (2006) pp. 63-88. 14. Yuichi Yanai, Kunihiro Hamada, and The equipment consists: Yoshio Shimizu; The liquid ammonia n micrometers (thickness), tensile testing machines (Alwetron), Mullens treatment of cotton fibers-The structural (bursting strength), Elmendorf (tearing resistance), Bekk, Bendtsen, PPS (smoothness/roughness), Gurley, Bendtsen, Schopper (air permeance), changes of cotton fibers under different Cobb (water absorptiveness), etc., methods of liquid ammonia removal, Sen’i Gakkaishi, Vol. 61, No. 11, (2005) pp. n crush tester (RCT, CMT, CCT, ECT, FCT), SCT, Taber and 36-44. Lorentzen&Wettre (bending 2-point method) Lorentzen&Wettre (bend- 15. LI Yan; Study on the linen fabric comfort ing 4-point metod and stiffness rezonanse method), Scott-Bond (internal bond strength), etc., and bacteria repellency, Suzhou Univer- sity, (2004) pp. 33-35. n IGT (printing properties) and L&W Elrepho (optical properties), ect., 16. Koichi G., Sreekala M. S., Gomes A., Kaji n power-driven press, fall apparatus, incline plane tester, vibration table T., Ohgi J.; Improvement of plant based (specialized equipment for testing strength transport packages), natural fibers for toughening green com- n atomic absorption spectrmeter for the determination of trace element posites - Effect of load application during content, pH-meter, spectrophotometer UV-Vis. mercerization of ramie fibers, Composi- tes: Part A, 37, (2006) pp. 2213-2220. 17. HUANG Wen-yu, ZHAO Min, ZHU Hu- Contact: i-zhen, ZHOU Xiang, Structure of ramie treated by liquid ammonia, Journal of INSTITUTE OF BIOPOLYMERS AND CHEMICAL FIBRES Donghua University (Eng. Ed.), Vol 23, ul. M. Skłodowskiej-Curie 19/27, 90-570 Łódź, Poland Elżbieta Baranek Dr eng. mech., No. 1 (2006) pp. 103-170. tel. (+48 42) 638 03 31, e-mail: [email protected]

Received 14.02.2009 Reviewed 22.12.2009

FIBRES & TEXTILES in Eastern Europe 2010, Vol. 18, No. 5 (82) 85