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Wawro D., Stęplewski W.; Producing of Continuous Cellulose Fibres Modified with Plant Proteins.FIBRES & TEXTILES in Eastern Europe 2010, Vol. 18, No. 6 (83) pp. 32-38.

IntroductionFor many years attempts have been made to modify cellulose fibres with a variety of proteins. In one of the oldest methods, casein is either added in the course of vis-cose preparation or the viscose is blended with an alkaline solution of casein, fol-lowed by the forming of fibres in an acidic bath [1]. The purpose of the modi-fication was to conform cellulose fibres to protein fibres, and to reduce produc-tion costs. Animal-derived proteins were

Producing of Continuous Cellulose Fibres Modified with Plant ProteinsAbstractPresented is a method of producing cellulose-protein fibres from modified cellulose dis-solved in aqueous sodium hydroxide, as well as from isolates of rape- and sunflower-de-rived proteins. Fibres were spun from alkaline cellulose-protein solutions in a coagulation bath containing sulfuric acid and sodium sulfate. Mechanical and morphological proper-ties of the protein-modified cellulose fibres are given. The fibres revealed a high water retention value (WRV) of up to 139 %. The concentration and kind of protein are the main factors influencing the stability of the spinning process and the mechanical properties of the resulting fibres. The morphology and structure of the fibres were investigated by means of the SEM and WAXS methods. Also presented are test results of microbiological activity against the Staphylococcus aureus bacterial strain.

Key words: modified cellulose, cellulose solutions, plant proteins isolates, cellulose-pro-tein fibres.

Dariusz Wawro,Włodzimierz Stęplewski

Institute of Biopolymers and Chemical Fibres,Łódź, Poland

contact: dariusz.wawro@ibwch.lodz.pl

mainly used, such as casein, keratin, collagen and fibroin (from silkworm co-coons); rarely plant proteins. Cellulose-fibroin fibres are spun from a spinning solution prepared by blending a viscose containing 9% of cellulose and 5% of NaOH with 10% of an aqueous fibroin. The addition of fibroin to cellulose fibres results in a decrease in their strength and increase in their linear mass [2]. Cellu-lose with fibroin can be dissolved in the cuproamine complex Cu(NH3)4(OH)2 [3, 4] and NaOH [2]. Examinations of a cellulose/fibroin film prepared from the cuproamine complex showed that bonds are formed between active groups of the singular polymer molecules in the solu-tion [3, 4]. The cellulose/fibroin film shows a higher moisture content and amount of amorphous regions in com-parison to a pure cellulose product.

Compatible solutions of cellulose and fibroin can be obtained in N-methylmor-pholine oxide (NMM0) [5]. Film cast from such a solution has good mechani-cal properties. Cellulose and fibroin also dissolve in the ionic liquid 1-buthyl-3-methylimidazolium chloride (BMIM-Cl) [6]. Film cast from a solution of cel-lulose with 20% of fibroin is amorphous and of lower strength [6].

The authors of this paper carried out re-search on the use of regenerated fibroin and keratin in the forming of cellulose fi-bres based on alkaline solutions of modi-fied cellulose [7, 8].

Harvesting oil plants has increased re-markably in Poland and other European countries. With the growing demand for bio-fuels, countries are leaving behind substantial amounts of proteins as by products. These can be used not only as

fodder but also as a material in technical applications. Considering that the com-position of aminoacides ( lysine, cysteine and methionine) in the proteins of rape and soy is similar, it may appear that the proteins of rape are suited to the modi-fication of cellulose fibres [9]. Protein isolates contain a substantial amount of macroelements like calcium, magnesium and phosphorus, as well as microele-ments like iron, zinc and copper [10].

Fibres spun from alkaline cellulose-pro-tein solutions are often presented as new types of cellulose fibres since they differ from typical cellulose varieties in their physical structure and other properties. Potential uses of the fibres are in apparel, filtration cloth and bacteriostatic sanitary products.

The objective of the present work was to evidence the suitability of protein iso-lates derived from rape and sunflower for the modification of cellulose fibres pre-pared from a modified cellulose directly dissolvable in aqueous alkalis. A further goal was to examine the impact of the kind and concentration of the protein in the spinning solution upon the mechani-cal, morphological and structural proper-ties of the cellulose-protein fibres, as well as to determine the antibacterial action of the fibres against the Staphylococcus au-reus bacterial strain.

MaterialsThe following materials were used in the research:n Cellulose pulp modified at IBWCh

according to the procedure described in EP 1317573, with an average mo-lecular mass of DPw=346, dissolvable in aqueous sodium hydroxide

33FIBRES & TEXTILES in Eastern Europe 2010, Vol. 18, No. 6 (83)

n Protein isolates from the seeds of rape and sunflower prepared at the Insti-tute of Technical Biochemistry of the Faculty of Biotechnology and Food Sciences of the Technical University, Łódź. The protein solutions contained 15% of protein and 5% of NaOH.

n Reagents made by POCh. S.A., Gli-wice, Poland were used in the prepa-ration of the solutions and coagulation baths as well as in the analyses.

MethodologyPreparation of the cellulose alkaline solutionA modified cellulose pulp with a 75% content of water was used in the prepara-tion of the cellulose solutions. An aque-ous sodium hydroxide solution with a concentration of 10.2% served as a sol-vent, in which zinc oxide was dissolved in an amount sufficient to attain the as-sumed zinc concentration in the solution of cellulose. The dissolution proceeded at 2°C – 12°C for 60 minutes. The zinc con-tent, calculated as ZnO, in the spinning solution was 1.3%. The solution was next filtered and deaerated at a temperature of up to 16°C. The cellulose solution thus prepared was blended with an alkaline solution of protein which contained 15% of protein and 5% of NaOH. Cellulose-protein fibres were spun from the pre-pared blend at 20°C.

Forming of cellulose-protein fibresFibres were spun on an experimental wet spinning line equipped with a spinning head holding a platinum/ rhodium spin-neret with 150 holes of 80 μm diameter.An aqueous solution of 17°C containing 110 g/l of sulfuric acid and 150 g/l of sodium sulfate constituted the coagula-tion bath. The tow of solidified fibres was led through a second trough with water at 85°C, in which a drawing rate of R = 30% was applied. Next the tow passed a third trough holding water at 40°C. Then the fibres were tension-dried in two drying sections, each equipped with two heated godets of 40°C on the surface. The fibres were taken up at a speed of 30 m/min.

Analytical methodsThe cellulose content in the aqueous NaOH solution and the total alkalinity (sodium hydroxide and carbonate) were determined according to a description given elsewhere [11].

The method of measuring the clogging value Kw and corrected clogging value Kw* of the alkaline cellulose solution can be found in publication [12].

Images of the fibres cross-section and surface were taken by means of a scan-ning electron microscope – SEM/ESEM, Quanta 200 (W), FEI Co., USA.

The mechanical properties of the cel-lulose fibres were tested according to Standards PN-ISO-1973:1997 and PN-EN ISO 5075:1999 in an air-conditioned room at 65±4 % relative humidity and temperature of 20±2°C.

Samples of the fibres were mineralised with 70% HNO3 in a microwave oven to determine the content of zinc, which was measured in the mineralised residue by flame atomic absorption spectrometry (FAAS) at a wave length of 213.9 nm.

The antibacterial activity of the fi-bres against Staphylococcus aureus ATTC 6538 was tested quantitatively according to Standard JIS L 1902:2002. The number of bacteria grown after a 24 hour incubation in the fibres sample tested was estimated, as well as in cotton as reference.

Spectrophotometric spectra in the infra-red range were prepared with the use of FTIR apparatus of Unicam Co equipped with the control programme Winfirst ATI Mattson. Samples were prepared in the form of pressed cubes in potassium bromide (KBr Aldrich Co).The water retention value (WRV) was determined according to Standard ISO/FDIS 23714.

The rheology properties of the cellulose-protein solutions were measured by means of a digital viscometer – Brook-field model RV DV-II +, with the Rheo-calc V3.1-1 programme, at a temperature of 20°C, 25°C & 30°C.

The fibres were subjected to wide- an-gle x-ray diffractometry examination – WAXS – by means of a URD-6 dif-fractometer (Seifert Co.) in the reflection mode. The diffraction curves prepared were divided into crystalline peaks and amorphous components. The degree of crystallisation was calculated by a modi-fied version of the Hindelecha-Johnsona method [13,14]. The average size of the crystallites was calculated according to the Scherrer equation with the use of a WAXSFIT programme [15].

The Kiejdahl method was applied to de-termine the nitrogen content in the fibres.

The relative flammability of the fibres, expressed by the LOI index was tested according to standard PN-EN ISO 4589 – 2:2006.

Results and discussion The miscibility of the alkaline solu-tions of cellulose and plant protein was utilised in the preparation of protein-modified cellulose fibres. Both solutions can be blended at ambient temperature in a defined range of weight proportion. Alkaline cellulose-protein solutions are stable at ambient temperature and suit-able for spinning at conditions typical for the spinning of cellulose fibres. In the process described herein, an additional chemical treatment was not employed.

Impact of the kind and concentration of the protein in the cellulose solution upon its properties.The cellulose content in the solution was in the range of 5.15-6.35%., while the to-tal alkalinity was kept in the 7.16-7.84%.range. The apparent dynamic viscosity was measured at 10°C of the cellulose solutions. The corrected clogging value Kw* is an essential coefficient character-ising the filterability of the solution and stability of the spinning process. Alkaline

Table 1. Properties of the alkaline cellulose-protein solutions.

Symbol of solution

Kind of protein

Concentration of protein,

wt%

Concentration of cellulose,

wt%

Total alkalinity,

wt%

Dynamic viscosity at temp. 10°C,

mPas

Clogging value

Kw Kw*

C-1 – – 6.35 7.84 17250 1230 105

CP-1Sun-flower

0.47 5.82 7.74 7600 1988 178

CP-2 0.89 5.56 7.71 7625 3326 296

CP-3 1.26 5.25 7.63 5600 4192 361

CP-4

Rape

0.53 5.15 7.16 6250 – –

CP-5 0.76 5.15 7.66 5750 – –

CP-6 1.26 5.56 7.53 4000 – –

34 FIBRES & TEXTILES in Eastern Europe 2010, Vol. 18, No. 6 (83)

solutions of cellulose show the most fa-vourable corrected clogging value Kw*. Depending upon the amount of protein introduced, alkaline cellulose-protein solutions are characterised by a lower cellulose content, lower total alkalinity and lower apparent dynamic viscosity. Higher amounts of the protein introduced result in lower viscosity and an increased clogging value.

The main properties of the solutions from which cellulose-protein fibres were spun are shown in Table 1. Distinct differences in the amount of particles can be seen between the micro-scopic images of cellulose-, protein-and cellulose-protein solutions. The image of the cellulose solution reveals a few small particles with a size of up to 3µm ( proba-bly mechanical impurities), and a rhomb-like crystal. More numerous and larger are the particles in the colloidal protein solution. The particles of rape proteins are larger than those of sunflower. It seems that the particle size depends upon the kind of protein. Essential differences also appear in the images of the cellu-

lose-protein solutions. In the solutions with rape protein, large protein agglom-erates emerged in the course of blending. The solutions thus prepared were not fil-tered, hence fragments of protein may be expected to appear in the cross-section of fibres. In the solution with sunflower pro-tein, uniformly distributed particles are visible. It may be concluded that the type of protein used has a definite influence on the quality of the alkaline cellulose-protein solution.

Examination of the rheology of the cellulose-protein solutionsThe rheology of the solutions was exam-ined at 20, 25 and 30°C to compare the properties of the solutions and to establish a temperature suitable for fibres spinning. Figure 1 a-c present the impact of the shearing rate and temperature upon the apparent dynamic viscosity of alkaline solutions without a protein content and of those modified with sunflower or rape protein. Flow curves were drawn for an increasing and decreasing shearing rate.

A non-newtonian chara cter of the alka-line solutions of modified cellulose may

be concluded from the diagrams. Two basic groups can be discerned regardless of the kind of protein added. To the first group solutions may be qualified whose viscosity at 20 and 25°C decreases with increasing shearing rate and for which the run of the flow curves at increasing and decreasing shearing rate coincidence. Such cellulose solutions reveal pseudo-plastic fluid characteristics (thinned by shearing) typical for polymer solutions [16]. Increasing the solution temperature from 20 to 25°C causes a distinct de -crease in the apparent dynamic viscosity.As regards the second group of cellulose solutions, examined at 30°C, they show a hysteresis in the flow curves for both the ups and downs of the shearing rate. The arrows in the figures indicate the direction of change in the shearing rate. The solu-tions reveal anti-thixotropic fluid charac-teristics, in which the apparent viscosity increases at a constant shearing rate after a particular time. The viscosity depends on the time of shearing, hence these solu-tions are unstable in respect of rheology.

The anti-thixotropic character at shear-ing is related to the building of a mo-

4000

3000

2000

100020 40 60 80 120 140

Shear rate, 1/s

App

aren

t dyn

amic

vis

cosi

ty, m

Pas

20°C

25°C

30°C

1000

4000

3000

2000

100020 40 60 80 120 140

Shear rate, 1/s

App

aren

t dyn

amic

vis

cosi

ty, m

Pas

20°C25°C30°C

1000

Figure 1. Dependence of the apparent dynamic viscosity on the shearing rate and temperature of alkaline cellulose solution C-1 (a), modified with sunflower protein – symbol CP-3 (b), modified with rape protein – symbol CP-5 (c).

8000

7000

6000

5000

4000

300010 20 30 40 50

Shear rate, 1/s

App

aren

t dyn

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vis

cosi

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Pas

20°C

25°C

30°C

60

a) b)

c)

35FIBRES & TEXTILES in Eastern Europe 2010, Vol. 18, No. 6 (83)

lecular structure. The phenomenon observed at 30°C in the flow curves of the alkaline cellulose solutions is prob-ably connected to the initiation of gel formation. Hysteresis is particularly pronounced in the flow curve of the cel-lulose solution modified with sunflower protein (Figure 1b). With this protein, a temperature increase of the cellulose solution from 25 to 30°C does not result in a lowering of the apparent dynamic viscosity, which is not the case for rape protein-modified cellulose solutions or solutions without protein.

The spinning of fibres from alkaline solu-tions of protein-modified cellulose is ac-complished at about 20°C, hence the stao-bility of the solutions at that temperature, confirmed by rheology examination, is quite important considering the long last-ing process of fibres formation.

Mechanical properties of the cellulose-protein fibresTable 2 (see page 36) illustrates the im-pact of the protein concentration in a solution of cellulose on the mechanical properties of fibres and their nitrogen content. Comparison of the properties of cellulose fibres with those of the pro-tein modified ones shows a higher linear mass of the latter in the range of 3.02-3.62 dtex, as well as lower tenacity, ranging from 11.2 to 15.4 cN/tex. The elongation at break amounts to 5.1-9.4 %, largely depending upon the amount of protein added and drying conditions. The increase in linear density aroused interest, suggesting that further investi-gation of the drawing process should be undertaken. Research on the formation of fibres from alkaline cellulose solu-tions documented that the reorientation of tension-dried fibres usually increases the arrangement of both crystalline and amorphous regions, causing a distinct increase in tenacity along with a low-ered elongation at break. Presumably the lower tenacity of cellulose-protein fibres can be related to the macrostruc-ture of the fibres and the inconsistency of the fibres interior, which may cause local inner tensions. Analysis of the fi-bres cross-section in Figure 2 supports such an explanation. The image shows fragments of protein, the structure of the core layer and the developed brim of the fibres cross-section.

Fibres prepared from cellulose solution show the highest tenacity, which corre-

Figure 2. SEM images of the surface and cross-section of cellulose fibres – (a, b), cellulose-protein fibres modified with rape protein – (c, d) and cellulose-protein fibres modified with sunflower protein – (e, f, g).

a) b)

c) d)

e) f)

g)

sponds well with the good stability of the solution and its low corrected clogging value Kw*. Fibres spun and dried under tension are characterised by an elonga-tion at break of 9.2% and tenacity of 18.7 cN/tex.

Increasing the protein content in the spin-ning solution results in a higher nitrogen content in the fibres. The highest nitrogen content appears in fibres marked F CP-3 and F CP-6. The high nitrogen content could have been the reason for the dis-

36 FIBRES & TEXTILES in Eastern Europe 2010, Vol. 18, No. 6 (83)

tinctly lowered tenacity (11-15,4 cN/tex) and elongation.

Chemical and morphological struc-ture of the cellulose-protein fibres.It may be assumed that when the stream of cellulose and protein undergoes so-lidification, a difference appears in the diffusion speed of the solvent molecules and coagulating substance. In the course of solidification, the protein may be de-posited on the cellulose matrix, leading

to the forming of bonds between the polymers. It appeared from the spinning trials that the fibres formed are insuffi-ciently solidified and prone to mechani-cal damage; for example, an excessive squeezing of wet fibres causes the re-moval of a part of the proteins in the pressed out bath, which may result in a reduction in the nitrogen content in the fibres of up to 15%. It is only the dry-ing which completes the forming of the structure, conferring adequate mechani-cal strength upon the fibres. Figure 3

Table 3. Selected properties of the cellulose-protein fibres.

Symbol of fibres

Kind of protein

Nitrogen content,

%WRV,

%LOI,%

Zinc content,mg/kg

F C-1 – – 116 17.8 8.2

F CP-1

Sunflower

0.4 123 – –

F CP-2 0.8 134 18.4 116.3

F CP-3 1.4 139 18.4 217.8

F CP-4

Rape

0.5 – – –

F CP-5 0.8 127 – –

F CP-6 1.4 133 19.3 184.2

Table 2. Impact of the protein concentration in the solution of cellulose on the mechanical properties of fibres and their nitrogen content.

Symbol of fibre

Kind of protein

Symbol of cellulose solution

Linear density,

dtex

Tenacity, conditioned,

cN/tex

Elongation at break,

%

Nitrogen content,

%F C-1 – RC-1 2.57 18.7 9.2 –

F CP-1

Sunflower

CP-1 3.06 15.4 9.4 0.4

F CP-2 CP-2 3.23 12.9 7.6 0.8

F CP-3 CP-3 3.36 11.2 5.1 1.4

F CP-4

Rape

CP-4 3.02 14.6 7.8 0,5

F CP-5 CP-5 3.30 13.1 6.5 0.8

F CP-6 CP-6 3.62 12.5 9.4 1.4

Figure 3. FTIR spectra of cellulose and cellulose-protein fibres modified with sunflower protein, denoted as F CP-3 (N = 1,26%), F CP-2 (N = 0,89%), F CP-1 (N = 0,47%), and FC-1 (N = 0%).

0,3

0,25

0,2

0,15

0,1

0,05

04000

Wavenumber, cm-1

3500 3000 2500 2000 1500 1000 500

Abs

orba

nce

ZOOM

FCP-1FCP-2FCP-3FC-1

presents the FTIR spectra of cellulose and cellulose-protein fibres.

Analysis of the cellulose-protein fibres modified with sunflower protein reveals amide I bonds (oscillating extension vi-brations C = O, 1600-1690 cm-1) at a wave length of 1633-1644cm-1 that distinctly correlate with the nitrogen content in the fibres. Similarly, amide II bonds (exten-sion vibrations CN = O and bending vi-brations NH 1480-1575cm-1) at a wave length of 1508-1517cm-1 correlate with the nitrogen content in the fibres [17].

The presence of amide I and II bonds in cellulose-protein fibres enables the formation of hydrogen bonds with wa-ter [18]. All this is confirmed by the in-crease in WRV, which depends upon the content of nitrogen in the fibres, and by the change in absorbance at wave lengths corresponding to inter and intra hydrogen bonds i.e. 2900 & 3450cm-1.

Figures 2a and 2b show SEM images of the surface and cross-section of cellu-lose fibres. The surface is smooth, with-out distinct recesses and flaws (Fig. 2a magnification-2000x). The fibres have an oval cross-section (Fig. 2a, 4000x).

In Figure 2c the surface of cellulose-pro-tein fibres modified with rape protein is shown at a magnification of 3000x. The picture reveals a distinctly developed brim with deep flaws and protruding oval protein agglomerates. The outer layer on the circumference of the fibres is about 1-2 μm thick. In the cross-section of the fibres (Fig. 2d), an irregular core is seen that has a fine granular structure with ap-parent protein inclusions. For compari-son, a cross-section of fibres modified with sunflower protein is also presented (Fig. 2e, f, g 2000x and 4000x), in which some irregular dark objects can be seen. A developed brim does not appear de-spite a comparable nitrogen content. There are, however, fragments of the pro-tein confined in the fibres’ interior. The cross-section surface of a single fibres amounts to 220 to 280 μm2, while that of the protein fragments is in the range of 5 to 50 μm2, comprising a significant part.

Fibres of different nitrogen content, from about 0.4 to 1.4 %, were examined. A relation could be detected between the nitrogen content and zinc content in the fibres (Table 3), amounting to 217.8 mg/kg, which is evidence of zinc bonding in the course of fibres formation (zinc ap-

37FIBRES & TEXTILES in Eastern Europe 2010, Vol. 18, No. 6 (83)

pears in the cellulose-protein solution), which may influence the building of the fibres structure.

Assuming that the nitrogen content in the protein is equal to 6.25%, the cellulose fibres marked F CP-3 contain 8.75% of protein. The limiting oxygen index – LOI – of the cellulose -nitrogen fibres did not increase markedly, while the WRV in-creased by about 20% for fibres with a higher nitrogen content. The increase in zinc content in the fibres is closely relat-ed to the nitrogen content. In conclusion, the content WRV and zinc increases with an increase in the nitrogen content.

Examination of the cellulose-protein fibres by wide angle x-ray diffractom-etry – WAXSFibres with a varying nitrogen content modified with isolates of sunflower pro-tein (F CP-1, F CP-2, F CP-3) and with isolates of rape protein (F CP-6) were chosen for WAXS investigation. Results are presented in Table 4.

It can be concluded from Table 4 that the addition of sunflower protein has a dis-tinct impact on the content of the crys-talline phase of the fibres. It is, however, difficult to univocally define the relation-ship between the protein content and the crystallinity degree of the samples marked F CP-1, F CP-2 i F CP-3, since the lowest addition of the protein (Sam-ple F CP-1) increased the crystallinity by about 8%, whereas the highest amount of protein (F CP-3) decreased the crysr-tallinity by 6%, compared with unmodit-fied fibres. Such results may suggest that a concentration of the modifying protein

Table 5. Antibacterial activity of cellulose-protein fibres against Staphylococcus aureus.

Symbol of sample

Zinc content, mg/kg

Time,h

Amount of bacteria,U/sample

Activity

bacteriostatic baktericidal

F C-1 8.190 6.1 x 104 – –

24 1.6 x 107 – –

F CP-2 116.3 24

1.15 x 107 -0.2 -2.6F CP-3 217.8 2.88 x 102 1.4 -1.0

Table 4. Results of the diffraction investigation – WAXS – of the cellulose-protein fibres.

Symbol of fibres

Kind of protein isolate

Nitrogen kontent,

%

Degree of crystallinity,

%

Dimensions of crystallitesLhkl, A

101 10(-1) 002

F C-1*) – – 39.0 36.8 40.5 38.6

F CP-1

Sunflower

0.4 46.7 25.9 43.9 44.2

F CP-2 0.8 41.3 32.4 41.9 41.3

F CP-3 1.4 37.5 36.2 44.7 43.9

F CP-6 Rape 1.4 33.2 32.5 38.7 47.4

*) – cellulose fibres

Figure 5. WAXS curves registered for cellulose fibres F C-1 with development to crystalline peaks (Miller coefficients are marked) and amorphous components (A1 and A2).

100

80

60

40

20

010 20 30 40 50 60

cell-I

101

101 002

A1

A2 040, 311202

2theta [deg]

Inte

nsity

[a.u

.]

Figure 4. Comparison of WAXS curves of the cellulose-protein fibres.

100

80

60

40

20

010 20 30 40 50 60

2theta [°]

Inte

nsity

[a.u

.]

FC-1F CP-2F CP-1F CP-3F CP-6

exists which does not cause any change in the crystalline content in the cellulose fibres matrix.

Modification of cellulose fibres with rape protein (F CP-6) distinctly reduces the crystallinity degree.

The average dimensions of crystallites perpendicular to the plane point to physi-cal changes in the fibres structure under the influence of any of the additives. De-fining the character and reason for the changes occurring is rather difficult be-cause information concerning the protein isolates used is too scant.

Figure 4 and 5 present WAXS roent-genograms of the cellulose-protein fibres analysed.

Bioactivity of the cellulose-protein fibres

The cellulose-protein fibres were tested in respect of antibacterial activity against the Staphylococcus aureus bacterial strain, the results of which are given in Table 5. Fibres with the highest pro-tein content appear to be bacteriostatic against the aforementioned strain. The effect augments with an increasing con-tent of zinc in the fibres (F CP-3). Fibres spun by coagulating in an acidic bath with a low content of zinc (8,19 mg/kg) are neither bactericidal nor bacteriostatic.

The preliminary testing of their bioac-tivity suggest that the cellulose-protein fibres may be applied due to their content of zinc, for the manufacture of bioactive sanitary and medical materials.

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Conclusions1. The method of wet-forming cellulose-

protein fibres from an alkaline cellu-lose solution modified with isolates of plant proteins developed herein ena-bled the preparation of a new type of cellulose fibres characterised by a spe-cific physical and chemical structure.

2. The essential impact of the presence of protein in the spinning solution on the sorption properties of the fibres obtained was documented.

3. Stable alkaline cellulose solutions with a protein content in the range of 0,47-1,26% pave the way for the preparation of cellulose-protein fibres with an improved WRV of up to 139 %, a tenacity of up to 15.4 cN/tex and an elongation at break in the range of 5.1-9.4%. The fibres have a rather low limiting oxygen index – LOI – in the range of 18.4-19.3%.

4. Cellulose-protein fibres modified with rape protein of 1.4 % nitrogen content are characterised by a fibre cross- section with a developed brim and high content of large agglomerates of the protein.

5. Cellulose-protein fibres modified with sunflower protein of 1.4 % nitrogen content and 217.8 mg/kg zinc content reveal bacteriostatic activity against Staphylococcus aureus bacteria.

AcknowledgmentThe research was funded by the Minister of Science and Higher Education in 2007-2010 as research project no. N N508 3070 33.We would like to convey our warmest thanks to Professor Jadwiga Gołąbczak for the preparation of plant protein isolates. Techni-cal University of Lodz, Faculty of Biotechnol-ogy and Food Sciences, Institute of Techni-cal Biochemistry.We are also grateful to Dr Marcin Bączek for the x-ray analysis of the cellulose-protein fi-bres. University of Bielsko-Biała, Institute of Textile Engineering and Polymeric Materials, Dept of Physics and Structural Research.

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Received 6.04.2010 Reviewed 8.12.2010

83FIBRES & TEXTILES in Eastern Europe 2011, Vol. 19, No. 1 (84)

AcknowledgmentsThis investigation was carried out as part of the ProeTEX project entitled “Protection e-Textiles: MicroNanoStructured fi bre systems for Emergency-Disaster Wear”, supported by the European Commission within the Sixth Framework Program for Research and Tech-nological Development (contract no. 026987)

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Received 30.03.2010 Reviewed 20.09.2010

Institute of Biopolymers and Chemical Fibres

Multifi lament Chitosan Yarn

The Institute of Bioploymers and Chemical Fibres is in possession of the know- how and equipment to start the production of continuous chitosan fi bres on an extended lab scale. The Institute is highly experienced in the wet – spinning of polysaccharides, especially chitosan. The Fibres from Natural Polymers department, run by Dr Dariusz Wawro, has elaborated a proprietary environmently-friendly method of producing continuous chitosan fi bres with bobbins wound on in a form suitable for textile processing and medical application.

We are ready, in cooperation with our customers, to conduct investigations aimed at the preparation of staple and continuous chitosan fi bres tailored to specifi c needs in preparing non-woven and knit fabrics.

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For more information please contact:Dariusz Wawro Ph.D., Eng

Instytut Biopolimerów i Włókien Chemicznych ul. Skłodowskiej-Curie 19/27;

90-570 Łódź, Poland; Phone: (48-42) 638-03-68, Fax: (48-42) 637-65-01

E-mail: dariusz.wawro@ibwch.lodz.pl

Multifi lament chitosan yarn