Download as pdf or txt
Download as pdf or txt
You are on page 1of 7

Journal of Cleaner Production 65 (2014) 561e567

Contents lists available at ScienceDirect

Journal of Cleaner Production


journal homepage: www.elsevier.com/locate/jclepro

Reducing environmental pollution of the textile industry using keratin


as alternative sizing agent to poly(vinyl alcohol)
Narendra Reddy a, Lihong Chen b, Yue Zhang a, Yiqi Yang a, b, c, d, *
a
Department of Textiles, Merchandising & Fashion Design, 234, HECO Building, East Campus, University of Nebraska e Lincoln, Lincoln, NE 68583-0802,
USA
b
Key Laboratory of Science and Technology of Eco-Textiles, Ministry of Education, Donghua University, Shanghai 200051, China
c
Department of Biological Systems Engineering, 234, HECO Building, East Campus, University of Nebraska e Lincoln, Lincoln, NE 68583-0802, USA
d
Nebraska Center for Materials and Nanoscience, 234, HECO Building, East Campus, University of Nebraska e Lincoln, Lincoln, NE 68583-0802, USA

a r t i c l e i n f o a b s t r a c t

Article history: Keratin from chicken feathers used as warp sizing agents on polyester/cotton blends and polyester
Received 22 March 2013 provide similar sizing performance compared to poly(vinyl alcohol) and are also easily degradable in
Received in revised form activated sludge. Poly(vinyl alcohol) (PVA), the most common sizing agent is not degradable in textile
27 September 2013
effluent treatment plants. Efforts to find substitutes to PVA that can provide similar sizing performance,
Accepted 28 September 2013
Available online 8 October 2013
be biodegradable and cost-effective have not been successful. In this research, keratin was studied as
potential sizing agents for polyester and polyester/cotton materials and the sizing performance was
evaluated in comparison to PVA. Keratin provided similar cohesion and strength improvements but had
Keywords:
Biodegradation
low abrasion resistance on polyester/cotton fabrics. Keratin in activated sludge showed a substantial
Polyvinyl alcohol decrease in Chemical Oxygen Demand (COD) whereas there was a negligible decrease in COD for PVA.
Sizing Overall, the low cost and biodegradable keratin exhibited potential to replace PVA.
Keratin Ó 2013 Elsevier Ltd. All rights reserved.
Chicken feathers

1. Introduction (PVA) for synthetic fibers and blends have been the preferred sizing
agents. Relatively low price, good performance properties and easy
Textile processes such as sizing and desizing consume consid- biodegradability are the advantages of starch whereas PVA is
erable amounts of water, energy and chemicals and are mostly preferred for the excellent sizing performance and easy desize-
responsible for the toxic effluents released into the environment ability although PVA is more expensive than starch. However, PVA
from textile plants (Moore and Ausley, 2004; Du et al., 2007). accounts for 45% of the total BOD load but does not degrade in
Textile industry is one of the largest consumers of water in the textile effluent treatment plants and is reported to persist in water
world. For instance, processing a ton of textiles is estimated to released from treatment plants (Ren, 2000; Savin and Butnaru,
consume about 80e100 m3 of water that is subsequently released 2008). Attempts to recover and reuse PVA and other sizing agents
into the environment (Fu et al., 2011; Hamilton and Chiweshe, and limit their release into the environment have been technically
1998; Hebeish et al., 2008). Several reports have highlighted the challenging and/or economically unviable (Sun et al., 2012; Sarkar
problems and concerns on processing textiles and their effects on et al., 2012).
the environment (Fu et al., 2011). Most countries, especially in the Substituting PVA with sizes developed from biopolymers has
European Union have enacted several regulations to limit the been attempted to reduce the environmental impacts of PVA.
environmental impacts of textile processing. Among the various Starch has been modified by grafting with acrylates to make starch
textile processes, sizing and desizing account for 40e60% of the more suitable for sizing synthetic fibers and their blends (Zhu and
effluent load in a textile mill (Hebeish et al., 2006). Traditionally, Cheng, 2008; Zhu et al., 2008). In another report, starch was grafted
starch and starch derivatives for cotton and poly(vinyl alcohol) with methacrylates and sized on cotton, polyester and polyester/
cotton (P/C) yarns and found that a proper grafting ratio was
necessary to achieve good tensile properties (Zhu and Cao, 2004).
* Corresponding author. Department of Textiles, Merchandising & Fashion
Design, 234, HECO Building, East Campus, University of Nebraska e Lincoln, Lincoln,
Other biopolymers such as cyclodextrans and chitosan have also
NE 68583-0802, USA. Tel.: þ1 402 472 5197; fax: þ1 402 472 0640. been studied as potential sizing agents (Hebeish et al., 2006, 2008;
E-mail address: yyang2@unl.edu (Y. Yang). Stegmaier et al., 2008).

0959-6526/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jclepro.2013.09.046
562 N. Reddy et al. / Journal of Cleaner Production 65 (2014) 561e567

Ability to form films, adhere to fibers, provide flexibility and easy manufacturers in the United States to compare the properties of the
removal from the fibers after weaving are some of the most desirable feather sized materials. PVA 1 was a fully hydrolyzed copolymer
features of a sizing agent. Starch and PVA are preferred for sizing due with a molecular weight (Mw) of approximately 65 kDa. Viscosity
to their good sizing performance and relatively easy desizeability of PVA 1 at 20  C was 11.6e15.4 mPas at 4% solid content. PVA 2
although enzymes are used to remove starch based size. Plant pro- containing 80e85% PVA had a hydrolysis value between 88 and 96%
teins such as wheat gluten and soy proteins have been made into and a viscosity of 14e25 mPas for 4% solid content at 20  C. Sodium
films for food and medical applications, used as adhesives for various hydroxide and other chemicals required for the study were ob-
applications and also made into regenerated protein fibers for textile tained from VWR international, Bristol, CT.
and medical applications (Reddy and Yang, 2011a). Proteins have
also been used as adhesives for composites and wheat gluten has 2.2. Preparation of the keratin sizing solution
been studied as a binder for textile printing paste (Reddy and Yang,
2011b; Hamilton and Chiweshe, 1998). These properties make plant Feathers were pre-treated in alkaline solution to dissolve the
proteins suitable for sizing applications. We have recently demon- feathers and obtain keratin. Pre-treatment was done by heating the
strated that plant proteins such as soy proteins and wheat gluten and feathers in alkaline solution (0.25e1%) at 90  C for 30 min. After
chicken feathers used as sizing agents on cotton, polyester and heating, the solution was filtered, pH of the solution adjusted be-
polyester/cotton provide similar performance properties to PVA and tween 8 and 10 and the solution was reheated to 90  C. The rovings
were also easily degradable in activated sludge (Chen et al., 2013a,b; and yarns wound onto frames were placed in shallow plates and
Reddy et al., 2013; Yang and Reddy, 2013). sized at 90  C for 5 min. After sizing, the materials were allowed to
Similar to plant proteins, poultry feathers have also been stud- dry at 21  C and 65% relative humidity. Fabrics were also sized
ied for various non-food applications. Feathers or keratin from similarly, except that after sizing, the fabrics were passed through a
feathers have been made into fibers, composites, films, sponges, laboratory padder to ensure constant pick-up and penetration of
hydrogels for various end-uses (Reddy and Yang, 2010; Hill et al., size into the fabrics. PVA based sized were applied onto the rovings,
2010). Unlike plant proteins, feathers do not have food applica- yarns and fabrics based on the manufacturers recommended con-
tions and their non-food applications are also limited. About 1.8e2 ditions (heating 1e2% PVA in water and sizing at 90  C).
million tons of chicken feathers are available in the United States A two-step pre-treatment was used to prepare the sizing solu-
and most of the feathers are disposed in landfills. However, unlike tion for polyester rovings. Since extraction of keratin from the
plant proteins, it is difficult to dissolve feathers and develop feathers required higher concentrations of alkali (up to 100% by
products. Most of the previous applications have used feathers in weight of feathers), considerable amounts of acid (hydrochloric
their original form (reinforcement for composites) or extracted acid) was added to reduce the pH of the solution to 7e9 after the
keratin from feathers to be processed into films, hydrogels and fi- initial pre-treatment. Addition of the strong acid into the strong
bers (Huda and Yang, 2008; Wang et al., 2012). The large availability alkali solution resulted in formation of salts in the solution. After
and virtually no cost makes feathers attractive raw material for sizing, salt on the polyester rovings caused high moisture sorption
sizing textile yarns. However, appropriate methods of dissolving during conditioning and decreased the mechanical properties
feathers and the ability of feather to provide the desired considerably. To decrease the amount of salts in the sizing solution,
improvement in strength and abrasion resistance need to be a two-step pre-treatment was used. Initially, feathers (10%) were
investigated. soaked in 1% NaOH for 12 h at room temperature. Feathers were
In this research, keratin from chicken feathers was used to size later washed thoroughly in warm water to remove the alkali until
polyester and polyester/cotton yarns. Effects of size preparation the pH of the feather was 7. Later, the keratin obtained were dried
conditions and amount of size (add-on, %) on the tensile properties and used for sizing by treating with 0.25% alkali for 1 h at 95  C.
and abrasion resistance of rovings and yarns were studied. Biode- Sizing of the roving was done as described earlier. Samples were
gradability of keratin solutions in activated sludge and the ability of dried in an oven at 105  C for 3 h and their dry weight was deter-
keratin to be desized were also investigated. Commercially avail- mined before and after sizing. Amount of size (add-on, %) on the
able PVA based sizing agents were used to evaluate the perfor- materials was calculated based on the difference in weight of the
mance of keratin as sizing agent. samples before and after sizing using Equation (1).

2. Materials and methods Add  on; % ¼ ½ðWa  WbÞ=Wb  100 (1)

2.1. Materials where, Wa is the dry weight of the samples after sizing and Wb is
the dry weight of the samples before sizing.
Whole chicken feather consisting of quills, barbs and barbules Viscosity of the sizing solution was determined on a Brookfield
were supplied by Feather Fiber Corporation (Nixa, MO). Feathers (R/S plus) rheometer using a CC-25 spindle and cup. Measurements
were ground into powder using a Wiley mill and used for alkaline in terms of mPas were taken with solution concentration between
hydrolysis. Sizing was done on rovings to measure the cohesion 0.25 and 2% for 1 h, maintaining the temperature of the solution at
between fibers, on yarns and fabrics to determine the changes in 90  C using a water bath.
strength and abrasion resistance due to sizing. Polyester/cotton
(65/35) rovings (70s Hank) and yarns (15s Ne) were supplied by 2.3. Property evaluation
Mount Vernon Mills, Mauldin, S.C. Cotton used in the P/C blend was
strict low middling with average length of 27 mm. Polyester fibers 2.3.1. Cohesion test
in the blend were of 1.4 denier, 38 mm cut length, breaking tenacity Ability of the size to adhere to the fibers was evaluated in terms
of 6.5 g/den and 27.8% elongation. Polyester (100%) rovings and of cohesive strength of the rovings. Since rovings are a loose as-
yarns used in the study were supplied by Shuford Yarns LLC, sembly of fibers that have almost no strength, increase in roving
Hickory, NC. Fabrics (P/C type 7435) and 100% polyester (Dacron strength would be a good indicator of the adhesion/cohesion be-
type 54) were purchased from Test Fabrics Inc., West Pittston, PA. tween fibers (Stegmaier et al., 2008) Tensile properties of rovings
Two types of commercially available PVA based sizes (named PVA 1 were tested on an MTS tensile tester (MTS Corporation, Eden
and PVA 2) were obtained from major sizing chemical Prairie, MN, Model: Q Test 10) using a load cell of 500 N and
N. Reddy et al. / Journal of Cleaner Production 65 (2014) 561e567 563

Fig. 3. Comparison of the performance of the P/C and polyester rovings at different
Fig. 1. Influence of concentration of alkali used during pre-treatment on the tensile humidities. Sizing was done at 90  C for 30 min and the add-on (%) was 10%.
properties of the polyester and P/C rovings. Feathers were pre-treated at 90  C for
30 min, pH of the solution during sizing was 8 and the add-on (%) on the roving was 65% relative humidity for about 48 h before being peeled off from
10%. Data points having statistically significant difference have been represented with
different alphabets.
the plates. Films were tested for tensile strength and elongation on
an MTS tensile tester according to ASTM standard D 882. At least 10
traverse speed of 50 mm min1 and gauge length of 10 cm. Yarn sample each from three separately cast films were tested and the
strength was measured on an Instron tensile tester (Model 4444) average and  one standard deviation were reported.
using a gauge length of 10 cm and crosshead speed of 18 mm min1.
At least 25 samples from each condition were tested and each 2.3.4. Biodegradation
experimental condition was repeated three times. Average and  2.3.4.1. COD and BOD5. Biodegradability of the keratin solutions in
one standard deviation between the three experiments were activated sludge was evaluated by measuring the changes in
calculated and reported here. Chemical oxygen Demand (COD), 5-day Biochemical Oxygen De-
mand (BOD5) and total and ammonia nitrogen. COD and BOD5 were
2.3.2. Abrasion resistance measured according to the American Public Health Association
Abrasion resistance was measured on both fabrics and yarns. Standards. Activated sludge was collected from the local waste
Sized fabrics were tested for abrasion resistance on a CSI Universal water treatment plant and acclimatized in the laboratory for 48 h.
Wear Tester using “0” emery sand paper. Standard weight of 454 g Keratin and PVA solutions (300 ppm) were prepared and about
for the polyester fabrics and 227 g for the P/C fabrics were used. 35 ml of activated sludge collected from the waste water treatment
plant was added along with nutrient buffers. COD of the diluted
2.3.3. Film properties activated sludge added into the keratin and PVA solutions was low
Keratin films were prepared by heating 6% feather in 0.25% alkali (about 20 mg L1) to ensure that the sludge did not interfere with
solution at 95  C for 1 h. After heating, the pH of the solution was the biodegradation measurements. Treatment of the keratin and
adjusted to 8 and the solution (200 g) was cast onto Teflon coated PVA solution was continued for up to twelve days and oxygen was
plates. Glycerol (10% on weight of feathers) was added to reduce the pumped into the containers to maintain the aerobic conditions.
brittleness of the keratin films. The solution was dried at 21  C and Samples were taken about every 24 h from the containers and the

Fig. 2. Influence of pH of the sizing solution on the tensile properties of the polyester Fig. 4. Comparison of the abrasion resistance of the polyester and P/C fabrics treated
and P/C rovings. Feathers were pre-treated at 90  C for 30 min using 0.5% NaOH and with keratin and PVA at different add-on (%). Sizing was done at 90  C for 30 min and
the add-on (%) on the roving was 10%. Data points having statistically significant dif- the pH of the keratin solution was 8. In each curve, data points with different alphabets
ference have been represented with different alphabets. denote statistically significant difference.
564 N. Reddy et al. / Journal of Cleaner Production 65 (2014) 561e567

COD, BOD5 and total and ammonia nitrogen were determined. COD
was determined according to US EPA Standard 8000 reactor
digestion method using the HACH test kit (TNT plus 822). BOD5 was
determined by measuring the concentration of dissolved oxygen
before and after incubation for 5 days in the dark at 20  C. Con-
centration of the PVA and keratin for the BOD5 tests was also
300 ppm and it was ensured that the dilution water used had an
oxygen consumption of less than 0.2 mg L1. Nutrient buffers were
added as prescribed in the standard procedures.
2.3.4.1.1. Total and ammonia nitrogen. Total and ammonia ni-
trogen released from the feather keratin during degradation in
activated sludge was measured to determine if the keratin would
impede the biodegradation. An alkaline persulfate oxidation
digestion method was used to determine the ammonia content. In
this method, salicylate and hypochlorite in an alkaline a sodium
nitroferricyanide buffer turn the effluent water green and the in-
tensity of the color is proportional to the amount of ammonia in the
sample. To determine the amount of nitrogen released during
Fig. 5. Comparison of the biodegradation of chicken feather keratin and PVA
degradation, about 50 g L1 of salicylic acid and potassium sodium (300 ppm) in activated sludge measured in terms of the changes in the COD and BOD5.
tartrate each, 0.32 mol L1, 10 g L1 of sodium nitroferricyanide and
sodium hypochlorite solution (3.5 g L1 active chlorine, 3.2. Viscosity of the sizing solution
0.75 mol L1 free alkali) were added. After addition the sludge was
allowed to stand for 1 h at room temperature and samples were Pre-treating the chicken feathers in various concentrations of
drawn and measured for absorbance at 697 nm in a spectropho- alkali at 90  C for 30 min dissolved the feathers and provided keratin
tometer (Beckman Coulter, CU 920). At least three samples were solution with viscosity of 1.5 mPas compared to 2 mPas for PVA. The
drawn for each time point and a calibration curve prepared with viscosity of the keratin solution was considerably lower than that of
known concentrations of nitrogen were used to determine the ni- chitosan (20e140 mPas) suggesting that higher concentrations of
trogen released due to the degradation of the feathers. keratin solution could be used for sizing (Stegmaier et al., 2008).
To determine total nitrogen, samples drawn from the activated
sludge containing keratin were added with 40 g L1 of potassium 3.3. Effect of alkali concentration
persulfate,15 g L1 of sodium hydroxide and the samples were digested
at 120  C for 40 min. The digestion was terminated by adding 1 ml HCl Keratin obtained using higher concentrations (1%) of alkali
and the absorbance of the solution at 220 and 275 nm were measured provided considerably lower strength to both the P/C and polyester
on a spectrophotometer. Concentration of the total nitrogen was rovings as seen from Fig. 1. Considerable hydrolysis of the feathers
calculated based on the absorbance values using a calibration curve. occurred when 1% NaOH was used and therefore the strength of the
rovings was lower compared to the respective strength at 0.25 and
0.5% alkali. A similar trend was also observed for the elongation of
3. Results and discussion the rovings. Although alkali concentrations lower than 0.25% may
increase the strength of the rovings, feathers did not dissolve
3.1. Film properties completely when the alkali concentration was lower than 0.25%.
Compared to plant proteins such as soy proteins and wheat gluten
Keratin films obtained in this research had a low breaking load that were studied as potential sizing agents, much higher concen-
of 1 MPa, elongation of 1.3% and modulus of 334 MPa compared to tration of alkali was required to dissolve the feathers since feathers
PVA films that had much higher breaking stress (24.3  3.9 MPa) are highly crosslinked with cysteine linkages (Chen et al., 2013a,b).
and elongation (278  34%). Inferior strength and elongation of the
keratin films should mainly be due to the lower molecular weight 3.4. Effect of pH of sizing solution
and hydrophilicity of the keratin compared to PVA. Although ker-
atin films were considerably weaker and brittle compared to PVA pH of the sizing solution affected the tensile strength and
films, keratin had good adhesion to the fibers, especially cotton and elongation of polyester rovings but the properties of the P/C rovings
therefore provided better sizing performance as discussed below. did not show any significant change with changes in pH as seen
from Fig. 2. Both strength and elongation of the polyester roving
Table 1 were lower at pH 7 and increased with increasing pH up to 10.
Comparison of the desizing ability (size removal) of the feather keratin and PVA on Considerable amounts of acid were added to obtain pH 7 sizing
polyester and P/C fabrics under various desizing conditions. solution after pre-treatment with 0.5% NaOH. Addition of the acid
Type of Desizing conditions % Size removed into the alkaline solution resulted in the formation of salt which
fabrics
Temp Time, Water to fabric ratio # Of
changes the attraction between the proteins and the fibers and also

C min rinses makes the proteins more hydrophilic. Therefore, there would be
Washing Rinsing Keratin PVA
less binding (cohesion) between the polyester fibers and feathers at
Polyester 90 5 5:1 5:1 1 92.63.7 76.7  4.6 pH 7 and the higher amounts of moisture on keratin would also
5:1 5:1 2 99.4  0.5 95.7  3.8
reduce the attraction towards the hydrophobic fibers leading to
10:1 5:1 1 97.8  3.8 99.4  1.0
20 5 10:1 5:1 1 100 61.5  3.4
lower strength and elongation. At high pH (11), there is little salt
P/C 90 5 5:1 5:1 1 89.8  4.0 77.0  4.3 and considerable repulsion between the fibers and the protein
5:1 5:1 2 99.3  1.2 100 solution and therefore lower strength and elongation. A pH range of
10:1 5:1 1 100 100 8e10 was found to be most suitable for sizing polyester with
20 5 10:1 5:1 1 95.1  2.6 82.3  3.9
feather keratin. P/C rovings were relatively unaffected by the pH of
N. Reddy et al. / Journal of Cleaner Production 65 (2014) 561e567 565

with keratin was lower compared to PVA as seen from Fig. 4. There
was a continual increase in abrasion resistance with increase in add-
on (%) but the increase on polyester fabrics was considerably higher
compared to the same fabrics treated with PVA. Even at a percentage
add-on of 1.9%, the polyester fabrics treated with keratin had sub-
stantially higher resistance of 660 cycles. Further increase in add-on
up to 6% did not show any appreciable increase until about 8% add-
on when the abrasion resistance increased to 1035 cycles. Contrary
to the changes in abrasion resistance seen on polyester fabrics, the P/C
fabrics treated with keratin had lower abrasion resistance than PVA
treated fabrics at all the add-ons (%) studied. Highest abrasion resis-
tance obtained on P/C fabrics treated with keratin was 99 cycles (add-
on 8.3%) compared to 250 cycles for PVA at an add-on of 7.6%. Abrasion
resistance is related to the film forming properties of the sizing so-
lution. Since there was low attraction between the hydrophilic keratin
and hydrophobic polyester fibers, most of the sizing solution would
have remained on the surface forming a thick film when the solution
was dried. Cotton in the P/C fabrics would have absorbed the sizing
Fig. 6. Total and ammonia nitrogen released from the feather keratin during degra- solution and the solution had penetrated inside with relatively
dation in activated sludge.
thinner film on the surface. Therefore, the polyester fabrics treated
the sizing solution because cotton had good attraction to the ker- with keratin had higher and the P/C fabrics lower abrasion resistance
atin solution at all the pHs studied. compared to PVA. This result is contrary to the roving strength im-
provements where the polyester rovings had lower and the P/C rov-
ings similar strength compared to PVA. Poor attraction and therefore
3.5. Effect of humidity on tensile properties
poor adhesion between polyester and keratin causes the polyester
rovings to have lower strength but the film formation on the surface
Relative humidity had a significant influence on the strength
provides good abrasion resistance.
and elongation of both polyester and P/C rovings treated with
keratin as seen from Fig. 3. While the strength of the P/C roving
3.7. Desizing
increased with increasing humidity, the strength of the polyester
rovings decreased at high (75%) humidity. Similar trend was
Size applied onto fibers should be easily removed (desized) after
observed for the elongation of the rovings. At low humidity (55%),
weaving. Desizing of starch is done using enzymes whereas PVA
the keratin films on the fibers are brittle and therefore the rovings
can be desized using hot water (70e90  C), one of the benefits of
have lower strength and elongation. Increasing humidity increases
using PVA as warp size (Du et al., 2007). Ideally, size removal must
moisture on the films and provides better flexibility to the rovings
be >90% and should not require additional chemicals and high
leading to higher strength and elongation. However, when the
temperature. As seen from Table 1, keratin can be easily desized
humidity if 75%, there is probably excessive moisture on keratin
from both polyester and P/C fabrics with low amounts of water
that increased the repulsion between the hydrophobic polyester
even at room temperature. A 100% removal of keratin was observed
and hydrophilic proteins. This could decrease the strength and
for polyester fabrics when desized at 20  C for 5 min with a fabric to
elongation of the polyester rovings at 75% humidity.
water ratio of 1:10 compared to 62% removal for PVA under similar
desizing conditions. Alternatively, complete removal of the size was
3.6. Abrasion resistance also obtained when the desizing was done at 90  C for 5 min but
using 1:5 ratio of water and two rinses. In the case of P/C fabrics,
Keratin size on polyester fabrics provided substantially higher size removal varied from 90 to 100% depending on the temperature
abrasion resistance whereas abrasion resistance of P/C fabrics treated and washing and rinsing conditions used. A desizing efficiency of
95% was obtained when the fabrics were treated at 20  C for 5 min
with a fabric to water ratio of 1:10 compared to 82% removal for
PVA. Keratin was easily desized from both the polyester and poly-
cotton fabrics without using high temperatures or large amounts
of water suggesting that sizing with keratin would save energy,
reduce costs and benefit the environment.

3.8. Biodegradability

Poor degradability of PVA in textile waste water treatment


plants is the primary reason for the efforts to find biodegradable
substitutes. As seen from Fig. 5, PVA had marginal decrease in COD
from 399 mg L1 to 308 mg L1 after treating in activated sludge for
3 days whereas the keratin solution showed continued decrease in
COD until 12 days. There was a 70% decrease in COD for the keratin
solution and a 30% decrease for the PVA solution during the period
studied. PVA size had an initial BOD5 of 17 mg1 and reduced to
2 mg L1 after three days of degradation suggesting that there was
Fig. 7. Comparison of the performance of the keratin size on P/C and polyester rovings no further biodegradable material left in the PVA size. In the case of
at different add-on (%) with two different commercially available PVA based sizes. keratin, the BOD5 before treating in the sludge was 76 mg L1 and
566 N. Reddy et al. / Journal of Cleaner Production 65 (2014) 561e567

continued to decrease to 5 mg L1 after 12 days. Although the COD lower add-on. Since keratins can be derived from coproducts with
values for keratin were considerably lower than that of PVA, there limited use and at almost no cost and the size preparation only used
was some non-biodegradable material present in the feathers since alkali solution, the keratin size would still be highly competitive
the COD values was more than 100 mg L1 after 12 days of degra- price-wise to PVA even if higher add-on (%) are required.
dation and when the BOD5 was lower than 100. Addition of fresh
sludge into the keratin solution after 6 days did not result in further 4. Conclusions
decrease in COD also suggesting that some portion of the keratin
was non-biodegradable. However, the concentration of the sludge Keratin obtained from chicken feathers after treating with alkali
used for biodegradation in this study was considerably low was found to be highly effective as sizing agents. At similar add-on
compared to the levels existing in textile effluent plants and a much (%), abrasion resistance of polyester fabrics treated with keratin was
higher concentration of PVA and keratin (300 ppm) than found in considerably higher but P/C fabrics were lower compared to PVA.
textile waste water treatment plants was used in the study. Our results demonstrate that cohesion between fibers is more
Therefore, under practical sizing conditions, it is anticipated that critical to obtain good improvement in strength and the ability of
keratin would be easily degradable in textile waste water treatment the sizing solution to form films on the surface influences the
plants based on the changes in COD and BOD5 observed. abrasion resistance. Keratin solutions were easily biodegradable in
Presence of high levels of proteins is reported to be undesirable activated sludge and there was negligible release of total and
in waste water treatment plants due to the inhibition of microor- ammonia nitrogen. Overall, chicken feather keratin as warp size
ganisms by the ammonia released from proteins during degrada- would be inexpensive, biodegradable and provide good sizing
tion. Fig. 6 shows the amount of total and ammonia nitrogen performance and therefore be ideal substitute to PVA.
released from the keratin during the 6 days of treatment in acti-
vated sludge. There is a sharp decline in the total nitrogen after Acknowledgments
treating in the sludge for up to 3 days and the total nitrogen later
stabilized. A corresponding increase in ammonia nitrogen was seen The authors thank Agricultural Research Division, Multi-State
until day 4 and then the ammonia nitrogen released from the Project S1054 (NEB37-037), USDA Hatch Act at the University of
keratin decreased sharply. It should be noted that the amount of Nebraska-Lincoln and Chinese National High Technology Research
total and ammonia nitrogen released is negligible and should not and Development Program 863 Project (2013AA06A307), the
inhibit the biodegradation of the sludge. Based on the changes in Doctoral Dissertation Innovation Program BC201040, Fundamental
COD, BOD5, total and ammonia nitrogen, it is clear that feather Research Funds for the Central Universities (No. 2011D10543) of
keratin had considerably better biodegradation in activated sludge Donghua University for providing the financial support to complete
compared to PVA demonstrating the potential to replace PVA for this work. Living expenses provided by the China Scholarship
textile warp sizing and offers a potential solution to decrease the Council for Lihong Chen are also gratefully acknowledged.
sizing related pollution from the textile industry.

References
3.9. Comparison of the performance of chicken feather keratin as
size with PVA Chen, L., Reddy, N., Yang, Y., 2013a. Remediation of environmental pollution by
substituting poly(vinyl alcohol) with biodegradable warp size from wheat
Fig. 7 provides a comparison of the tensile strength of the P/C gluten. Environ. Sci. Tech. 47, 4505e4511.
Chen, L., Reddy, N., Yang, Y., 2013b. Soy proteins as environmentally friendly
and polyester sized rovings treated with feather keratin and two sizing agents to replace poly(vinyl alcohol). J. Environ. Poll. Res. 20 (9),
commercially available PVA based sizing agents. P/C rovings sized 6085e6095.
with feather keratin provided similar strength compared to PVA 1 Du, G., Liu, L., Song, Z., Hua, Z., Zhu, Y., Chen, J., 2007. Production of polyvinyl
alcohol-degrading enzyme with Janthino-bacterium sp. and its application in
and higher strength than PVA 2 but at a relatively higher add-on %.
cotton fabric desizing. Biotechnol. J. 2, 752e758.
Highest strength provided by PVA 1 on P/C rovings was 225 N at an Fu, Z., Zhang, Y., Wang, X., 2011. Textiles wastewater treatment using anoxic filter
add-on of 13% and 176 N at an add-on of 10% for PVA 2. Keratin bed and biological wriggle bed-ozone biological aerated filter. Bioresour.
Technol. 102, 3748e3753.
solution provided a highest strength of 217 N at an add-on of 18%
Hamilton, L.E., Chiweshe, A., 1998. Textile pigment printing binders prepared by
but the strength was relatively low (111 N) at add-on of 10%. Higher modifying wheat gluten with methyl acrylate. Starch/Stärke 50, 213e218.
amount of keratin solution was required to provide strength Hebeish, A., Aly, A.A., El-Shafei, A.M., Zaghloul, S., 2008. Innovative starch de-
improvement comparable to PVA because of the lower strength and rivatives as textile auxiliaries for application in sizing, finishing and floccula-
tion. Starch 60, 97e109.
elongation of the keratin films compared to PVA films. Hebeish, A., Higazy, A., El-Shafei, A., 2006. New sizing agents and flocculants
Strength improvement provided by the keratin solution on derived from chitosan. Starch 58, 401e410.
polyester rovings was slightly inferior compared to both the PVAs Hill, P., Brantley, H., Dyke, M.V., 2010. Some properties of keratin biomaterials:
kerateines. Biomaterials 31, 585e593.
studied. At similar add-on (10e11%), the rovings sized with keratin Huda, S., Yang, Y., 2008. Composites from ground chicken quill and polypropylene.
had strength of 169 N compared to 190 N for PVA 1 and 188 N for Compos Sci. Technol. 68 (3e4), 790e798.
PVA 2. Lower strength provided by the keratin solution on the Moore, S.B., Ausley, L.W., 2004. Systems thinking and green chemistry in the textile
industry: concepts, technologies and benefits. J. Cleaner. Prod. 12, 585e601.
polyester rovings should be due to the poor attraction between Reddy, N., Yang, Y., 2010. Light-weight polypropylene composites reinforced with
polyester and keratin. Since the roving strength is a measure of whole chicken feathers. J. Appl. Polym. Sci. 116, 3668e3675.
cohesion between fibers, poor attraction means less binding and Reddy, N., Yang, Y., 2011a. Potential of plant proteins for medical application. Trends
Biotechnol. 29 (10), 490e498.
therefore lower strength. Although PVA size provided higher Reddy, N., Yang, Y., 2011b. Completely biodegradable soyprotein-jute biocomposites
strength of the rovings, the difference between PVA and the keratin developed using water without any chemicals as plasticizer. Ind. Crops Prod. 33,
size under the optimize condition was about 20N which may not be 35e41.
Reddy, N., Zhang, Y., Yang, Y., 2013. Corn distillers dried grains as sustainable and
significant in terms of performance on the weaving machines. In
environmentally friendly warp sizing agents. ACS Sustainable Chem. Eng..
addition, the commercial sizing agents contain additives such as http://dx.doi.org/10.1021/sc4002017.
plasticizers, preservatives and stabilizing agents that help to Ren, X., 2000. Development of environmental performance indicators for textile
improve the performance properties. Such additives could also be process and product. J. Cleaner Prod. 8, 473e481.
Sarkar, A., Sarkar, D., Gupta, M., Bhattacharjee, C., 2012. Recovery of polyvinyl
added into the keratin size to improve the performance properties alcohol from desizing wastewater using a novel high-shear ultrafiltration
on polyester and/or to obtain similar increase in strength but at module. CLEAN 40 (8), 830e837.
N. Reddy et al. / Journal of Cleaner Production 65 (2014) 561e567 567

Savin, I., Butnaru, R., 2008. Wastewater characteristics in textile finishing mills. Yang, Y., Reddy, N., 2013. Potential of using plant proteins and chicken feathers for
Environ. Eng. Manag. J. 7 (6), 859e864. cotton warp sizing. Cellulose 20 (4), 2163e2174.
Stegmaier, T., Wunderlich, W., Hager, T., Siddique, A., Sarsour, J., Planck, H., 2008. Zhu, Z., Cao, S., 2004. Modifications to improve the adhesion of crosslinked starch
Chitosan-a sizing agent in fabric production development and ecological eval- sizes to fiber substrates. Text. Res. J. 74 (3), 253e258.
uation. CLEAN 36 (3), 279e286. Zhu, Z., Cheng, Z., 2008. Effect of inorganic phosphates on the adhesion of mono-
Sun, W., Tian, J., Chen, L., He, S., Wang, J., 2012. Improvement of biodegradability of phosphorylated cornstarch to fibers. Starch 60, 315e320.
PVA-containing waste water by ionizing radiation pretreatment. Environ. Sci. Zhu, Z., Lin, X., Long, Z., Wang, Y., 2008. Adhesion, film and anti-flocculation
Pollut. Res. 19, 3178e3184. behavior of amphoteric starch for warp sizing. AATCC Rev. 8 (4), 38e43.
Wang, S., Taraballi, F., Tan, L.P., Ng, K., 2012. Human keratin hydrogels support
fibroblast attachment and proliferation in vitro. Cell Tissue Res. 347, 795e802.

You might also like