EVALUATION OF DETERGENTS AND WASHING PROCESSES WITH ARTIFICIALLY SOILED FABRICS

Evaluation of Detergents and Washing Processes

Summary 3

1. Introduction 2. Standardization and Testing of Detergents and Laundering Processes 3. Influence Factors during the Washing Process
Table 1 - Factors Influencing the Washing Result

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4. Soiling Characteristics
4.1 4.2 5.1 5.2 5.3 5.4 5.5 5.6 6.1 6.2 6.3 6.4 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 Natural Soilings Table 2 - Classification of Soilings Artificial Soilings (Standards) Washing Effects Redepositions Bleaching Effect Enzyme Action Phases of Soil Removal Soil Removal Kinetics Assortment Table 3 - EMPA Test Soilings Manufacturing Control Storage Properties Principle Washing Process Table 4 - Specifications of EMPA Test Fabrics Detergent Water Ballast Laundry Test Materials Measurement of the Remission Values Statistical Evaluation

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5. Physical and Chemical Processes of Washing

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6. EMPA Test Fabrics

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7. Washing Tests with Artificially Soiled Fabrics

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8. Conclusions Literature

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Evaluation of Detergents and Washing Processes with Artificially Soiled Fabrics

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.

2. Standardization and Testing of Detergents and Laundering Processes

ISO standard 4319 1 contains guidelines determining the performance of detergents, but they are merely recommendations and there are no concrete instructions. According to ISO 4319, ASTM D 2960-84 2 and DIN 44'983 3, the performance of detergents and washing processes is tested with averagely soiled household laundry. Comparison in pairs or priority classification according to statistically stipulated test projects 3 and the visual aspect of cleanness are used for such assessments. Such tests with household laundry are expensive. ISO 4319 and ASTM D 2960-84 point out that there is no particular experimental arrangement comprising all the performance characteristics of a detergent. Within the scope of the International Electrotechnical Commission (IEC), test instructions for assessing the technical characteristics of washing machines 4 have been elaborated. Diverse national prescriptions 5 - 8 are based on these documents. For testing the cleaning effects, artificially soiled test fabrics, such as carbon black / olive oil (EMPA art. 101) and IEC strip (EMPA art. 105) with diverse soilings (see paragraph 6) are used.

3. Influence Factors during the Washing Process

The washing result depends on a great number of influence factors related to detergents, water, washing machine, solings and textiles. These influence factors are listed in table 1. Regarding the assessment of detergents and washing processes for their cleaning effect on textiles, it is advisable to limit the tests to usual washing conditions and fields of application and to include standard detergents, standard washing processes and standardized textiles for comparison. Suitable experimental arrangements help obtain reliable results and classifications. This allows to distinguish the efficiency of diverse categories of detergents, such as washing powders and liquids with and without phosphates, with and without perborate as well as diverse machine washing programs, such as pre-, main and gentle washing, filling proportions and so on. Specific test conditions will be required for more subtile differentiations regarding the development of product groups or washing programs and the optimizing of detergents and washing programs.

Table 1 - Factors Influencing the Washing Result 1. Detergent

Dosage

- Interfacially Active Compounds

Anionic active agents Non-ionic active agents Soap Cationic compounds

- 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.

5. Physical and Chemical Processes of Washing

5.1 Washing Effects The presence of interfacially active compounds (surfactants) and of inorganic components (builders) in detergents entails physical washing and soil removal processes known as washing effects. Active agents containing a liposoluble, lipophile and a watersoluble, hydrophile molecular share can emulsify water-unsoluble substances like fats and oils and disperse pigment soiling. Inorganic components such as soda, silicates and polymer phosphates intensify the adsorption on the fibre surface and the removal of soil particles. Sodium tripolyphosphate as well as organic compounds like nitrilotriacetate are polyvalent ions and most efficient builders for soil adsorption; they also dislodge alkaline earth from soil and fibres. 5.2 Redepositions Besides soil removal, the inversed process, i. e. redeposition, is actual and appears particularly in heavily soiled washing liquors. As a consequence, white fabrics turn grey. 5.3 Bleaching Effect Bleaching agents (perborate and chlorine bleach) react with soil and colour components on the fibres of the laundry and in the washing liquor, which produces the bleaching effect, also an important factor. 5.4 Enzyme Action

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.

6. EMPA Test Fabrics

6.1 Assortment EMPA offers the test soilings listed in table 3. IEC (International Electrotechnical Commission) has standardized the test strips (art. 105) for testing household performances of washing machines.

Table 3 - EMPA Test Soilings

1. Carbon Black / Oil Soilings Art. 101 Cotton fabric, soiled with carbon black / olive oil (EMPA standard soiling) Art. 104 Mixture fabric polyester / cotton 65 / 35, soiled with carbon black / olive oil Art. 106 Cotton fabric, soiled with carbon black / mineral oil (IEC soiling) Art. 107 Wool fabric, soiled with carbon black / olive oil 2. Special Soilings Art. 111 Cotton fabric, soiled with blood Art. 112 Cotton fabric, soiled with cocoa Art. 114 Cotton fabric, soiled with red wine Art. 115 Cotton fabric, dyed with immedial black Art. 116 Cotton fabric, soiled with blood / milk / carbon black Art. 117 Mixture fabric polyester / cotton 65 / 35, soiled with blood / milk / carbon black 3. Combined Wash Test Strips Art. 103 EMPA- Test strip consisting in 8 cotton cuts (12 x 12 cm), with diverse soilings (fig. 4) Art. 105 IEC-Test strip consisting in 5 cotton cuts (15 x 15 cm) : unsoiled (bleached, without optical brightener) and carbon black / mineral oil, blood, cocoa, red wine soilings

Strips, Art. 103

Soilings

Effects Soil redeposition, fluorescence of optical brighteners Washing effects Cleaning effects on organic pigments and proteine soilings

Cotton, white Carbon black / oil Blood Cocoa Blood / milk / carbon black Immedial black Raw cotton Red wine

Bleaching effects

Fig. 4 - EMPA Wash Test Strips (Art. 103)

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 : - for art. 106 in : - for art. 111 in : - for art. 112 in : - for art. 114 in : - for art. 115 in : - for art. 116, 117 in : 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. carbon black, olive oil, water, stabilizers and emulsifiers; carbon black, mineral oil, water, stabilizers and emulsifiers; pigs blood, stabilized; cocoa powder, sugar, milk, water; red wine; immedial black CBO; pigs blood (stabilized), milk, water, carbon black.

7. Washing Tests with Artificially Soiled Fabrics

7.1 Principle Tests with artificially soiled test fabrics are meant to be comparative and presuppose fabrics from the same soil production series, combined with a standard detergent and a standard washing process under exactly defined conditions. Testing a detergent or a washing process requires several fabrics with the same soiling in each washing cycle and several washing cycles, each with unwashed fabrics.

7.2 Washing Process

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
101 104 106 107 111 112 114 115 116 117

Remission Values
unwashed 15 11 15 20 13 24 45 30 10 2 2 3 3 2 2 3 3 2 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

Washing Process
1 2 1 3 2 2 1 1 2 4 2 4

approx. 9 - 12

Washing Process (see paragraph 7.2) 1 2 3 4 : : : : 95 C laundry, 5 g / l ECE detergent + 0.5 g / l sodium perborate 60 C laundry, 5 g / l ECE detergent 30 C laundry, 5 g / l ECE detergent 60 C laundry, 5 g / l detergent with enzyme additive

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.

7.7 Measurement of the Remission Values

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

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ISO 4319 - 1977, Guide for comparative testing of performance, 1977-07-15. 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. Norme franaise NFC 73-172 (1968). DIN 44'983, Prfungen von Waschmaschinen (1968). Svensk Standard SS 4330101, 1978-01-01. ISO 2267, Verification of certain effects of laundering; Preparation and use of unsoiled cotton control cloth, 1972-11-01. Brschweiler H. , Methods of testing the performance of washing machines. Tenside-Detergents 5 (1973), S. 229-238. SNV 198'861, Waschmethoden fr textile Flchengebilde (1971). 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. Verordnung ber Wasch-, Spl- und Reinigungsmittel (Waschmittelverordnung), 13. Juni 1977, EDMZ 814.226.22, Bern. DIN 5033, Farbmessung (1972). Griesser R. , Die farbmetrische Erfassung von Wascheffekten. Tenside-Detergents 12 (1975), S. 93 - 100. Brschweiler H. , Ueber die Prfung des Wasch- und Bleichvermgens von Waschmitteln an knstlich angeschmutzten Geweben. V. Internat. Kongress fr grenzflchenaktive Stoffe, Barcelona 1968.

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