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1. Introduction
4. Soiling Characteristics
4.1
Natural Soilings
Table 2 - Classification of Soilings
6
6
4.2
Washing Effects
Redepositions
Bleaching Effect
Enzyme Action
Phases of Soil Removal
Soil Removal Kinetics
7
7
7
7
7
8
8
6.1
Assortment
Table 3 - EMPA Test Soilings
8
8
6.2
6.3
6.4
Manufacturing
Control
Storage Properties
9
10
10
10
7.1
7.2
Principle
Washing Process
Table 4 - Specifications of EMPA Test Fabrics
10
10
11
7.3
7.4
7.5
7.6
7.7
7.8
Detergent
Water
Ballast Laundry
Test Materials
Measurement of the Remission Values
Statistical Evaluation
11
12
12
12
12
13
8. Conclusions
13
Literature
15
Summary
A description of testing the cleaning performance of detergents and washing processes, in
using artificially soiled fabrics, is given. Existing standard procedures for comparative testing of
detergents and household appliances using naturally soiled laundry and artificially soiled fabrics
are mentioned. The factors influencing washing results, such as composition of detergents,
water, washing time, temperature and mechanical action during the washing process,
furthermore the behaviour of natural and artificial soils, are described. The physical and chemical processes occurring during washing, such as soil removal, redeposition, bleaching, enzyme actions and kinetic processes of particulate soil removal are discussed. EMPA test fabrics, production, controls, storage and the use of artificially soiled swatches to test detergency
are described.
1. Introduction
Artificially soiled test fabrics help determine the cleaning performance of detergents and washing processes. The standard soilings are widely spread and detergent manufacturers use
them for developing and improving formulations, raw product manufacturers for assessing
diverse active agents, washing components, complex formers, enzymes, etc. and
manufacturers of washing machines for testing washing programs.
Test materials are useful for developing ecologically beneficial detergents or energy-efficient
washing programs.
Soiled and unsoiled test fabrics are further employed for washing controls in laundries, consumer tests and for quality comparison in test institutes.
Housewifes frequently ask : "Which is the most performing detergent ?" or "Which washing
program must I take ... ?" and express so the practical bearing of assessing washing
products and processes.
The following specifications deal with international standards, testing of detergents and
washing processes, influence factors of washing, behaviour of natural and artificial soilings,
manufacturing and criteria of test fabrics, comparative tests, assessment and examples of
results obtained with test soilings.
- Inorganic Components
Washing alkalis (soda, silicates)
Phosphates (sodium tripolyphosphate)
Ion exchanger (sodium aluminium silicate)
Bleaching agent (sodium perborate)
Stabilizer (magnesium silicate)
- Organic Components
Complex former (NTA, citrate, etc.)
Polymer polycarbonic acid
Optical brighteners
Solvent (alcohols)
Enzymes (proteases)
Bleaching activators (tetraacetylethylene diamine, etc.)
Greying inhibitors (carboxymethyl cellulose, hydroxyethyl cellulose, etc.)
2. Water
Quantity
Hardness, Ca 2 + / Mg 2 + proportion
Purity, heavy metal content
3. Washing Machine
Washing temperature (initial temperature, heating rate, maximum temperature)
Washing time
Washing mechanics (rotating speed, running and standing position and diameter of the drum,
laundry volume, amount of liquor, dimensions and weight of the textiles, fabric / fabric friction, foaming)
Pre-, main washing and rinsing
4. Soilings
Degree of soiling
Diverse types of soilings (see paragraph 4.1)
5. Textiles
Fibre materials
Natural fibres (cotton, wool, etc.)
Synthetic fibres (polyester, polyamide, etc.)
Regenerated synthetic fibres (viscose, acetate, etc.)
Type of fabric (cloth, knit cloth, etc.)
Finish, colouration
Making-up (dimensions, weight, etc.)
Besides primary washing effects (i. e. soil and stain removal after one washing), secondary washing effects after several washings, such as greying (redeposits of soil), calcareous deposits and damaged laundry (loss of tearing strength, chemical damages), must be
taken into consideration in washing tests. Unsoiled test fabrics (control cloth for laundering
processes) 9 are available for this latter purpose.
4. Soiling Characteristics
4.1 Natural Soilings
It appears (table 2) that the diverse soilings behave differently with washing. Whilst
water-soluble salts, for instance, are easily removed with water, oily and greasy
soilings are emulsified with the interfacially active components of the detergents or
dissolved with organic solvants. Pigment soilings are either removed mechanically,
dispersed or desorbed with builder elements, according to the size of the particles. This
factor is decisive, particularly if fine particles are involved, i. e. hydrophilic pigments
(such as metal oxides, earth, road dust) or hydrophobic pigments (such as soof, dust).
Protein containing soilings, such as blood, milk, etc., are hard to remove, if they are
denatured with heat and chemical influences (bleaching agents, for example). It has
further been observed that albumen containing soils and substances with carboxyl
groups fix themselves one with the other as well as on fibres which also contain carboxyl
groups (such as cotton). This sort of calcareous soilings and deposits is only
removable with more sequestrating alkaline earth linking agents. Furthermore,
bleachable soil like fruit, wine and tea stains can be removed with chemical bleaching
agents.
Table 2 - Classification of Soilings
- Water-soluble soilings (salts, perspiration, acids, etc.)
- Oil and fat stains (fats, oils, sebum, etc.)
- Pigment soilings
hydrophilic particles (metal oxides, road dust, earth, etc.)
hydrophobic particles (soof, squama, etc.)
- Protein soilings (blood, milk, sauce, pus, etc.)
- Calcareous soilings and deposits (calcareous deposits, soil incrustations, proteins, etc.)
- Fruit, vegetable, colour and rust stains, etc.
- Microorganisms (bacteria, fungi, spores, etc.)
4.2 Artificial Soilings (Standards)
The great variety of natural textile soilings is reduced, with artificially soiled fabrics, to
some few characteristic types. It appears that soilings of the same kind, for instance oils
and fats, bleachable substances (like fruit and tea stains), protein containing compounds
(like blood), have a similar washing behaviour. Artificially soiled fabrics allow to measure
the soil removal process and, thus, determine the relevant influence factors of washing.
The protein containing blood / milk / carbon black soiling (EMPA art. 116, for instance;
see paragraph 6) helps test the performance of enzymes (proteases); the bleaching effect of sodium perborate, combined with bleaching activators, can be determined with
the mainly bleachable red wine soiling (EMPA art. 114); the widely utilized carbon black /
oil soiling on cotton, wool or polyester / cotton fibres (such as EMPA art. 101, 107, 104)
allows to rate the washing performance of diverse active agents, resp. active agents /
builder systems, as well as the influence of washing temperature and mechanics;
mechanical effects are measurable with the cocoa pigment soiling (EMPA art. 112) and,
for seizing the sequestrating action of complex formers against the agents causing the
hardness of water and against calcium and magnesium, the blood soiling (EMPA art.
111) will be of interest. Bleaching agents and high temperatures can indeed denature
blood soilings, according to their age. A detailed evaluation of this latter factor is also
assured. Based on a certain knowledge about the behaviour of diverse standard soilings
and adequate experimental arrangements, the influence factors of washing can be
identified and connected accordingly.
Washing tests are admitted in laboratories with diverse instruments, equipments and
machines, clean or naturally soiled ballast laundry and as field tests including household,
hospital, hotel and professional laundries.
Proteolytic enzymes in detergents split the preptide links of the proteines and entail the
water solubility of proteine containing soil.
5.5 Phases of Soil Removal
The removal of pigment soilings from textile fibres is divided into three temporal phases :
- Wetting and swelling of fibres and soil
- Removal of the superficial soil
- Gradual removal of the remaining soil
Fig. 1 "carbon black / soil soiling" illustrates these steps. The soil coating on cotton
appears on the raster scan microscope pictures in fig. 2.
5.6 Soil Removal Kinetics
The removal of remaining soil (S) is proportioned according to the washing time logarithm (t), following the formula
S = a log t + b.
Factor a depends on the kind of pigment soiling, chemical and physical influence factors
as well as on the washing mechanics, whilst b is mainly subject to washing temperature.
With diverse washing temperatures, the remission values for increasing washing times
approximate parallel straight lines (fig. 3) 16. In order to obtain the same washing result,
the proportions of the influencing factors (chemistry, temperature, time, mechanics) may
be varied.
Soilings
Cotton, white
Carbon black / oil
Blood
Cocoa
Effects
Soil redeposition,
fluorescence of optical
brighteners
Washing effects
Cleaning effects on organic
pigments and proteine
soilings
Bleaching effects
Red wine
6.2 Manufacturing
For manufacturing test fabrics, duly pre-treated and bleached fabrics are stained with a
dye padder in an accurately prescribed soiling liquor and dried.
The soiling liquors for articles
- 101, 104, 107 consist in :
red wine;
6.3 Control
The diverse soilings are produced in quantities of 1'000 - 3'000 m each and stored during 3 weeks. Next, the remission values of the unwashed and standard washed fabrics
are measured every 60 m. According to our specifications listed in table 4, the fabrics
are tested for their conformity to the requirements (paragraph 7.2) Production series and
batch number (60 m) are indicated on the delivered lots. The cuts of combined wash test
strips with identical serial numbers come all from the same soil production series.
6.4 Storage Properties
Artificially soiled fabrics age fast and old soilings are hard to wash. They must be stored
well packed in the dark, without chemical influences (humidity, formaldehyde). Kept
under these conditions, the fabrics can be used in comparing tests for approx.
1 year.
The washing conditions regarding temperature, duration and mechanics must be defined
exactly. The tests can be effected with washing devices (Ahiba Terg. O-Tometer, vat
washing machine) at constant temperatures or with drum washing machines at programmable temperatures. It is therefore important to make sure that the mechanical
influence factors, such as fabric / fabric friction for example, correspond to practice.
Laundry containers with balls (Atlas Lauder-Ometer, Linitest) produce hardly controllable mechanical influences and, as a consequence, unreliable results.
With drum washing machines, the standard washing processes 11 of 40, 60 and 80 or 95
C (maximum washing temperature) are the most suitable. In this relation, it is advisable
to opt for the single bath method, same drum running and standing times, same liquor
and laundry proportions, which lead to more accorate, comparative results than using
pre- and main wash with diverse reversing cycles, filling and liquor proportions 4.
EMPA test fabrics are controlled in drum washing machines : drum contents 35 l, ballast
laundry (cotton, EMPA art. 221, 40 x 60 cm, 150 ppm CaCO3 water hardness, 15 l
washing liquor; initial temperature of washing liquor 15 3 C, heating rate 1.8 C/min. up
to 30, 60, resp. 95 C, maximum washing temperature maintained during 10 min., rinsing
cycles and whizzing; dosage of detergent 5 g/l (table 4)).
Table 4 - Specifications of EMPA Test Fabrics
Article
No
101
104
106
107
111
112
114
115
116
Remission Values
unwashed
standard washed
54 4
44 4
63 3
37 4
67 3
50 3
82 3
38 4
48 3
53 3
48 - 55
approx. 64
15
11
15
20
13
24
45
30
10
2
2
3
3
2
2
3
3
2
approx. 9 - 12
117
Washing
Process
1
2
1
3
2
2
1
1
2
4
2
4
:
:
:
:
Measuring Conditions
Elrephomat DFC 5, R 457 filtre ( : 460 nm) with UV barrier FL 46, reference standard according
to DIN 533 14.
7.3 Detergent
According to the IEC prescription 4, a standard detergent must be used. The dosage is
best added to the water flowing into the washing machine, in g/litre, and depends on the
water hardness 13.
7.4 Water
The water hardness is usually divided into degrees of hardness. In Switzerland, the ranges between 0 - 15 fH are considered as average and over 25 fH as hard. 25 fH
(French hardness) correspond to 250 ppm CaCO3 and 2.5 mmol/l. The average water
hardness in Switzerland lies around 25 fH and the Ca2+ Mg2+ mol proportion is 4 : 1.
This water hardness applies with washing tests.
According to IEC method prescription 12, water may be transformed in a conditioning
plant, either into soft or tap water by adding hardening chemicals (CaCl2 . 2H2O, MgSO4 .
7H2O, NaHCO3) or in gasifying CaCO3 and MgCO3 with carbon dioxide and forming the
alkaline-earth hydrogen carbonates (temporary water hardness). The dosage of the
detergent 13 and the washing results 14 depend on the water hardness.
7.5 Ballast Laundry
Washing tests can be effected with clean, soiled, new, used, similar or diverse laundry
articles, identical or different fibre materials, with dry or wet laundry, or with diverse load
quantities.
The degree of soiling influences the quantities of redeposition, the amount of washing and
bleaching agents to use and the foaming behaviour, whilst load proportions and dimensions of the laundry articles have an impact on the mechanical influence factors. Soil
and lime binding behaviour 10 differs between new and used laundry.
Naturally soiled or clean laundry ballast ought to be used in accordance with the purpose
of the tests. The IEC prescriptions presuppose clean laundry ballast 4.
7.6 Test Materials
Besides ballast laundry, artificially soiled fabrics are washed. At least two of these fabrics
must be added to each washing. As the process of soil removal happens to scatter in and
between the washing cycles, 1 strip per kg laundry and 3 - 10 washing cycles are
customary.
For rating secondary washing effects (redeposition, lime deposits, damages), unsoiled
fabrics can be added to the solid ones.
This operation requires optical measuring devices, such as Elrephomat DFC5, Datacolor
Elrepho 2000, Hunterlab D25, etc., combined with a xenon lamp, resp. standard illuminant
D65, and a UV barrier between light source and test fabric (so as to enable
measurements without UV prompting of the optical brighteners). The wave length of the
centre of gravity is set at = 460 nm and the device calibrated in using barium sulphate
(Zeiss, Order No 505882) with a known absolute spectral radiance concentration (see
DIN 5033) 14. For avoiding a transmission of the light, the fabrics are measured in four
layers. UV prompting of optical brighteners also helps determine the degree of whiteness
of white fabrics.
7.8 Statistical Evaluation
The measured remission values are evaluated statistically. This implies two measurings
on both sides of each soiled cut, i. e. 4 measurings in all (x1). The average value of each
single cut is calculated on this base (x), further averages taken of all the washing cycles
and the standard deviation determined :
s =
( x x)
n 1
Higher remission averages () and no overlapping of the standard deviations (s) of value
pairs (1) and (2) are considered as more favourable washing, bleaching or redeposition
results. Significant differences between the averages are determined with the
t-test according to Student 10.
Besides calculating the remission values, their increase
DR = Rwashed - Runwashed
is also comparable.
Fig. 5 presents the washing results (washing, bleaching and redeposition effects) taken
from a consumer's test on six floor washing machines. The differences and scatterings
between the remission values obtained with each of these washing machines are due to
diverse temperatures of pre- and main wash, proportions of the washing liquor and
mechanical influences.
Fig. 6 illustrates the comparison between a liquid detergent and a phosphate containing
complete detergent. The cleaning effect of the liquid detergent is less performing, as there
are neither "builders" nor bleaching agents. Only motor oil soiling makes the exception :
higher contents of surfactants and solvants wash of this kind of soil more efficiently.
8. Conclusions
Artificially soiled test fabrics help obtain reliable results with relatively simple test arrangements, with regard to the cleaning effect of detergents and washing processes.
The multitude of influence factors produced with washing presupposes, however, standardized
detergents, washing processes and textiles for the comparative tests.
The measurability of the accompanying specific effects of washing allows to optimize detergents and washing processes.
Literature
ASTM D 2960-84, Standard method of controlled laundering test using naturally soiled fabrics and household appliances. Annual Book of ASTM Standards 15 (1984), S. 591 - 596.
DIN 44'983, Teil 50, Waschmaschinen fr den Haushalt, Gebrauchseigenschaften, Vergleichende praxisnahe Prfung des Kochwaschprogramms mit Haushaltwsche (1982).
Methods for measuring the performance of electric cloth washing machines for household use. Publication
456 (1974), Modification No 1 (1980), Bureau central de la Commission lectrotechnique internationale
(CEI), 1, rue de Varemb, CH-1202 Genve.
SEV 4101 - 1974 and SNV 414'101. Leitstze zur Ermittlung des Gebrauchswertes elektrischer Haushaltwaschmaschinen, Schweiz. Elektrotechn. Verein, Seefeldstr. 301, 8008 Zrich.
ISO 2267, Verification of certain effects of laundering; Preparation and use of unsoiled cotton control
cloth, 1972-11-01.
10
Brschweiler H., Methods of testing the performance of washing machines. Tenside-Detergents 5 (1973),
S. 229-238.
11
12
Hard water to be used for testing the performance of some household electrical appliances. Publication
734 (1982), Bureau central de la Commission lectrotechnique internationale (CEI), 1, rue de Varemb,
CH-1202 Genve.
13
Verordnung ber Wasch-, Spl- und Reinigungsmittel (Waschmittelverordnung), 13. Juni 1977, EDMZ
814.226.22, Bern.
14
15
16
Brschweiler H., Ueber die Prfung des Wasch- und Bleichvermgens von Waschmitteln an knstlich angeschmutzten Geweben. V. Internat. Kongress fr grenzflchenaktive Stoffe, Barcelona 1968.