Indian Journal of Fibre & Textile Research

Vol. 37, December 2012, pp. 358-363

Almond shell as a natural colorant
zlenen Erdem mal
a
& Leyla Yldrm
Faculty of Fine Arts, Textile and Fashion Design Department, Dokuz Eyll University, Turkey
Received 1 December 2011; revised received and accepted 28 March 2012
Outer green of almond l has been used to extract natural dye for dyeing of wool, using different mordants such as iron
(II) sulfate, copper (II) sulfate and potassium dichromate. Exhaust dyeing method has been applied using premordanting and
simultaneous mordanting of fibres. It is observed that wool fibres can be dyed in different colours and depth of shades with
almond shell dye. Control sample dyed without mordant shows light fastness of 2-3 and good wash fastness of 4-5
(bleeding) and 3 (colour change). Various colours have been obtained without mordant or by using quite lower amount of
metallic mordant such as 0.8 % owf (0.16 g/L) and 2 % owf (0.4 g/L). All the samples exhibit satisfactory bleeding and
colour change values. Iron (II) sulfate ensures the best light fastness. Improved light fastness is obtained using above-
mentioned lower amounts of iron (II) sulfate and copper (II) sulfate. Potassium dichromate is found to be less effective than
iron (II) sulfate and copper (II) sulfate on the light fastness. Burgundy-reddish shades which are rare in natural dyes have
been obtained using this mordant. As a novel alternative and potential natural dye, almond shell extract can be used to get
various colours and shades with satisfactory fastness properties.
Keywords: Almond shell, Colour yield, Light fastness, Mordant, Natural dyeing, Wool

1 Introduction
World wide growing consciousness of using
ecofriendly products in daily life has generated
renewed interest of consumers towards the use of
natural fibres dyed with ecofriendly natural dyes
1
.
There are many plants in nature that can provide
natural dye to obtain great variety of shades on fibres.
Various studies have been carried out on extraction
and use of natural dyes by conventional and
alternative methods
1-11
.
Some of the natural dyes can form metal
complexes using metal salts and as a result provide
different colours. Commonly used mordants are alum
(used with cream of tartar, which helps in obtaining
colour evenness and brightness); iron or copper
(which saddens or darken the colours, gives green
shades); tin (used with cream of tartar, which blooms
or brightens colours, especially red, orange and
yellow); blue vitriol (which saddens colours and gives
green shades); chromium; iodine; potassium; and
sodium. Dyeing with mordants can give extreme
fastness properties and according to the type of the
mordant, different colours and shades with the same
natural dyestuff can be obtained
8-10
.
At present the production of natural dyes by direct
farming results in substantially high specific cost per
kilogram of plant material and per kilogram of dyed
material. New strategies are required to establish
technically and commercially competitive processes.
Ecofriendly procedures consider local plant sources.
A promising concept for production of natural dyes
with lower specific cost involves the use of different
plant sources for the extraction of natural dyes
11
, as
indicated below:

direct farming yields rather expensive plant
material which is not available from other sources
use of cheap by-products from agricultural
activities, e.g. bark from the timber industry or
leaves from abundantly available plants such as
deodar, jackfruit and eucalyptus
use of dyestuff-containing wastes, e.g. released
from the food and beverage industry free of
charge
11
.
Use of organic wastes as colorants is also an
essential issue in terms of ecology. It is reported that
organic wastes such as almond shell can be used to
absorb metals and organic substances in the waste
water treatment
11-13
. Almond is consumed as a valuable
food and its shells are huge amount of waste material.
Almond shell is the woody endocarp of the almond
__________
a
To whom all the correspondence should be addressed.
E-mail: ozlenen.ismal@deu.edu.tr
MAL & YILDIRIM: ALMOND SHELL AS A NATURAL COLORANT


359
fruit (P. Amygdalus L.). Almond shell is being used as
heavy metal adsorbent, dyes adsorbent, a rich source in
preparing activated carbons and a source for the
production of xylo-oligosaccharides, dietary
antioxidants. High performance liquid chromatographic
(HPLC) analysis reveals the presence of quercetin,
isorhamnetin, quercitrin, kaempferol-3-O-rutinoside,
isorhamnetin-3-O-glucoside and morin as the major
flavonoids in all extracts
14
. Phenolic compounds
(by HPLC), lipids (by solvent extraction), proteins
(by micro-Kjeldahl) and fibre content (by enzymatic-
gravimetric AOAC method) in almond shell

have been
analyzed and a combination of flavonols, flavan-3-ols,
hydroxybenzoic acids and flavanones are identified
15
.
The major almond flavonoids are (+)-catechin, (-)-
epicatechin, kaempferol, and isorhamnetin
16
. Figure 1
shows some colouring components available in almond
shell extract.
Almond is being cultivated in many regions of
Turkey. However, high quality almond growing in
Data-Mula (Aegean region of Turkey) is very
famous all over the world. It is found that the studies
on the use of its shell as a natural colorant in textile
natural dyeing are not available in the literature so
far. The focus of this study is to evaluate dyeing and
some fastness properties of colorant extracted from
the almond shell by using conventional mordants in
order to produce a new and potential natural dye
source.
2 Materials and Methods
2.1 Materials
Wool fibres (fineness 25.1 ), almond shell, iron
(II) sulfate, copper (II) sulfate and potassium
dichromate were used in this study.

2.2 Methods
Wool samples (2.5 g) were dyed with dye solution
prepared from almond shell by exhaust method
(50:1 liquor ratio) in the Ata brand IR laboratory
dyeing machine. Almonds were picked in July and
August. Their outer green shells were peeled and
dried by spreading on a clean, cool and air ventilated
place. Completely dried shells were crushed by
hammering until getting small pieces (2-5 mm).
Dyeing liquor was extracted by boiling 3 g crushed
almond shell in 125 mL water for 1 h. The solution of
this boiled extraction was filtered and the reduced part
due to the boiling was completed to 125 mL with
water. This solution was used for the experiment.
Dyeing was performed following premordanting and
simultaneous mordanting using iron (II) sulfate,
copper (II) sulfate and potassium dichromate. Sample
codes and process conditions for premordanting and
simultaneous mordanting are shown in Table 1.
Premordanting and subsequent dyeing were
conducted at 100 C for 1 h. Dyed samples were
finally washed and dried at room temperature.



Fig. 1 Structures of Quercetin A, Quercetin B, Morin, Kaempferol, Kaempferol 3-O- rutinoside, Isorhamnetin, Isorhamnetin
3-O- rutinoside and (+) Catechin [Quercetin A CI 75670, CI Natural Yellow 10, 13 & Natural Red 1; Quercetin B CI 75730,
CI Natural Yellow 10; Morin CI 75660, CI Natural Yellow 8,11); Kaempferol CI 75640, Natural Yellow 13,10; Isorhamnetin
3-O- rutinoside CI 75680, Natural Yellow 10; and (+) Catechin CI Natural Brown 3]
INDIAN J. FIBRE TEXT. RES., DECEMBER 2012


360
2.3 Colour Measurement
K/S, CIE Lab, and wash and light fastness values
were studied. Colour measurements were made by using
Minolta CM-3600d spectrophotometer (Illuminant D65
and the CIE 10 observer). K/S values were calculated
according to the Kubelka-Munk equation.

2.4 Determination of Colour Fastness
Light fastness and wash fastness were determined
using Xenotest Alpha instrument (Xsenon-arc lamb)
(ISO 105 BO2) and Linitest machine
(ISO105 C06 - at 40 C for 30 min) respectively.
3 Results and Discussion
3.1 Colour Measurement
K/S values of the samples indicate that the
concentration and kind of mordant, and mordanting
methods significantly affect the lightness, shade and
colour yield. Significant colour differences (E) are
also obtained. Table 2 shows significant colour and
colour yield differences, depending on mordants and
mordanting methods. Natural colour obtained without
mordant is shown in Fig. 2. Generally, the significant
variation in colour change is observed with the
mordant concentration of above 2 %.
Lightness of samples, premordanted with iron (II)
sulfate and dyed, significantly reduces as compared to
the control sample. However simultaneous
mordanting and dyeing exhibits higher lightness.
Simultaneous mordanting with potassium dichromate
and dyeing ensures the highest lightness values.
Generally, simultaneous mordanting and dyeing
results in higher lightness than that of the
premordanting method.
In case of premordanting method, firstly mordant
reacts with the fibre to a great extent and subsequently
the dye molecules form a complex with this structure
resulting in a relatively more stable dye-fibre bond.
Simultaneous mordanting is found to be time and
energy saving. However, it may generate a loss in dye
and mordant, causing colour yield reduction. Mordant
and dye partially may remain precipitating in the dye
bath before linking to the fibres by forming a complex
themselves. It means that some of dyes and mordants
are unused. In this study, the tendency of getting
Table 1 Conditions for premordanting and simultaneous
mordanting and dyeing
Sample code FeSO4
% owf
CuSO4
% owf
K2Cr2O7
% owf
Premordanting
PM 1 0.8 (0.16 g/L) - -
PM 2 2 (0.4 g/L) - -
PM 3 20 (4 g/L) - -
PM 4 - 0.8 (0.16 g/L) -
PM 5 - 2 (0.4 g/L) -
PM 6 - - 0.8 (0.16 g/L)
PM 7 - - 2 (0.4 g/L)
PM 8 - - 20 (4 g/L)
Simultaneous mordanting
SM 1 0.8 (0.16 g/L) - -
SM 2 2 (0.4 g/L) - -
SM 3 20 (4 g/L) - -
SM 4 40 (8 g/L) - -
SM 5 - 0.8 (0.16 g/L) -
SM 6 - - 0.8 (0.16 g/L)
SM 7 - - 2 (0.4 g/L)
SM 8 - - 20 (4 g/L)
SM 9 - - 40 (8 g/L)
SM 10 - - 60 (12 g/L)
Table 2 CIE Lab measurements, K/S values and colour shades
Sample L* a* b* E K/S value Colour
C (Control) 40.812 21.912 20.333 - 12.229 Dark coral shades/red cornelian
PM1 27.089 7.597 4.16 25.589 14.641
PM2 26.303 6.6595 3.732 26.873 15.577
PM3 28.108 5.736 5.157 25.562 15.998

Dark brown shades
PM4 35.689 16.459 17.123 8.142 17.064
PM5 37.648 11.043 17.649 11.634 19.673
Cinnamon-copper shades
PM6 28.915 20.19 8.321 16.994 15.571
PM7 31.028 20.765 9.98 14.291 14.99
PM8 31.994 18.757 12.454 12.239 14.288

Burgundy/reddish shades
SM1 44.592 8.695 9.661 17.563 7.995
SM2 38.631 5.119 5.452 22.543 9.845
SM3 42.411 2.897 11.599 21.064 13.925
SM4 40.889 1.783 10.012 22.621 15.793

Light grayish-ash and
greenish shades depending on
mordant concentration
SM5 40.812 21.912 20.333 12.012 18.318 Lighter cinnamon-copper shade
SM6 44.811 16.168 13.378 9.867 9.775
SM7 51.275 11.201 15.375 15.773 8.363
SM8 63.105 3.414 19.814 29.033 6.634
SM9 60.898 1.23 17.596 28.96 7.082
SM10 59.815 -1.552 17.805 30.3 8.945

Lighter burgundy, beige, light
greenish shades depending on
mordant concentration
MAL & YILDIRIM: ALMOND SHELL AS A NATURAL COLORANT


361
higher colour yield with premordanting method
supports this suggestion. It could be suggested that
mordanting method directly affects the kind and
stability of complex formed by the mordanting agent
and strength of the bond between dye and fibre,
resulting in difference in light absorption, reflectance
and fastness properties of the dyed material. On the
other hand, considering ecological issue, mordanting
method may affect residual amount of mordant-dye
complex and consequently content of the effluent.
Potassium dichromate gives quite different shades
depending on mordant concentration. Excess amount
of dichromate results in significant colour change and
colour yield reduction in simultaneous mordanting.
Most of the natural dyes give various shades of
yellow, khaki, brown, beige and green. Premordanting
and lower concentration (0.8 % owf-0.16 g/L) of
potassium dichromate results in much better colour
yield and burgundy/reddish shades which are unusual
for natural dyestuffs. Based on these colours,
alternative mordants, biomordants and techniques can
be examined in further studies. It is reported that 3.5 %
natural mordant (fresh petaloids of banana flowers)
and 1.5 % potassium dichromate show similar colour
fastness, shade and K/S values
17
.

3.2 Light Fastness
One of the most important drawbacks of natural
dyes is insufficient light fastness. Table 3 shows the
light fastness values of all the samples. Control
sample dyed without mordant has good level of wash
fastness values, while its light fastness is found to be
2-3. It is reported that iron mordanting generally
increases the fastness properties; an improvement in
light fastness after application of an iron mordant is of
particular interest
18
. The fastness of a mordant dye
depends on the mordant and mordanting method,
because different metal-dye complexes are formed,
which may differ in their stability to light. Cox-Crews


Fig. 2 Colour obtained in control fabric (dyeing without
mordanting )
Table 3 Wash fastness and light fastness of sample
Wash fastness
Colour change Bleeding
Sample

Acetate Cotton Nylon Polyester Polyacrylonitrile Wool
Light fastness
C 3 4-5 4 4-5 4-5 4-5 4-5 2-3
PM1 3-4 4 4 4 4 4 3-4 4-5
PM2 4 4-5 4-5 4-5 4-5 4-5 4-5 4-5
PM3 4 4-5 4-5 4-5 4-5 4-5 4 5
PM4 4 4-5 4-5 4-5 4-5 4-5 4-5 3-4
PM5 4-5 4-5 4-5 4-5 4-5 4-5 4-5 4
PM6 4 4-5 4-5 4-5 4-5 4-5 4-5 2-3
PM7 4 4-5 4-5 4-5 4-5 4-5 4-5 2-3
PM8 4-5 4-5 4-5 4-5 4-5 4-5 4-5 2-3
SM1 4 4-5 4-5 4-5 4-5 4-5 4-5 3-4
SM2 4 4-5 4-5 4-5 4-5 4-5 4-5 3-4
SM3 3 4-5 4-5 4-5 4-5 4-5 4-5 5 (darkening)
SM4 3 4-5 4-5 4-5 4-5 4-5 4-5 5 (darkening)
SM5 4-5 4 4-5 4-5 4-5 4-5 3 3
SM6 3 4-5 4-5 4-5 4-5 4-5 4-5 2-3
SM7 3 4-5 4-5 4-5 4-5 4-5 4-5 2-3
SM8 3 4-5 4-5 4-5 4-5 4-5 4-5 2-3
SM9 3 4-5 4-5 4-5 4-5 4-5 4-5 3
SM10 4-5 4-5 4-5 4-5 4-5 4-5 4-5 4-5
Light fastness rating1(very poor), 2 (poor), 3 (fair), 4 (moderate), 5(good), 6 (very good), 7 (excellent), 8 (outstanding).
Wash fastness rating1(very poor, 2 (poor), 3 (fair), 4 (good), 5 (excellent).
INDIAN J. FIBRE TEXT. RES., DECEMBER 2012


362
studied on 18 yellow natural dyes and concluded that
the mordant is more important than the dye itself in
determining the light fastness of coloured textiles.
Use of tin and alum mordants results in significantly
more fading than chrome, iron or copper
19
.
Iron (II) sulfate exhibits the best light fastness values.
Low concentrations of iron (II) sulfate and copper (II)
sulfate improve the light fastness. While premordanted
samples with iron (II) sulfate have the light fastness of
4-5, it is necessary to increase the mordant concentration
to get light fastness of 5 in simultaneous mordanting and
dyeing. Potassium dichromate is found to be less
effective than iron (II) sulfate and copper (II) sulfate on
light fastness. Increase in concentration and type of
mordanting methods with potassium dichromate do not
improve light fastness. However, the light fastness of
4-5 is obtained by using a quite higher concentration
(60 % owf -12 g/L) of potassium dichromate. If the light
fastness values of 2-3 are satisfactory for the end user,
much lower concentration is sufficient to obtain
interesting burgundy-reddish shades which are rare in
natural dyes.

3.3 Wash Fastness
Wash fastness values of the samples are shown in
Table 3. All the colour changes and bleeding values
are found to be satisfactory; even it is relatively
comparable. Although no great difference exists
between wash fastness values, in some cases one
degree higher value can be obtained with the increase
in mordant concentration. However, it could be
debated whether this increase is worth of using higher
amount of mordant. Simultaneous mordanting and
dyeing with iron (II) sulfate have one degree less
colour change value than that of premordanting and
dyeing. The control sample without mordant has a
colour change of 3 and a bleeding of 4-5 and a light
fastness of 2-3. From this point of view, if the light
fastness is of no importance, use of mordant could be
omitted or various colours can be obtained by using
less amount of mordant. High colour fastness to
washing, even in the absence of any mordant, is the
consequence of presence of ionic attraction and
non-polar van der Waals interaction between
colouring component and protein fibres
20
.

4 Conclusion
4.1 Wool fibres can be dyed with outer green shells
of almond by using lower concentrations (0.8 % owf-
0.16 g/L) of iron (II) sulfate, copper (II) sulfate and
potassium dichromate mordant with satisfactory wash
and light fastness values. Concentration and kind of
mordant, premordanting and simultaneous mordanting
have a significant influence on colour, nuance and
colour differences. All the samples show good bleeding
and colour change values. The control sample dyed
without mordant also results in good wash fastness
(bleeding 4-5, colour change 3) and light fastness of 2-
3. If the light fastness is not essential for the end-user,
dyeing without mordant could be preferred or various
interesting colours with quite lower amounts of
mordant can be obtained. Iron (II) sulfate is more
effective than copper sulfate and potassium dichromate
and ensures the best light fastness values.
Burgundy/reddish shades which are rare and interesting
for natural dyes have been achieved by using lower
concentrations of potassium dichromate.
4.2 The use of this huge amount of waste material
(almond shell) is of importance in terms of ecology
and economy. Almond shell can be considered as a
novel potential and alternative natural colorant source
having an economical value. Industrial applications
and alternative techniques can be examined in further
studies.

Acknowledgement
Authors are thankful to the Tbitak (Scientific and
Technological Research Council of Turkey) for
providing financial support to this project
(No: 111M433) and to Dr. Necdet Seventekin,
Dr. Esen zdoan and Dr. Ayegl Ekmeki Krl
for their contribution in fastness and colour
measurements at the Textile Engineering Department
of Ege University.

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