Wet cleaning of historical textiles: surfactants and other wash bath additives gnes Tmr-Balzsy Abstract The paper

is a review of the literature relating to the use of water, surfactants and other additives for cleaning historical textiles. thical considerations are introduced and the common types of soil that occurs on historical textiles are characterized. The review covers pu!lications on the advantages and disadvantages of wet cleaning and discusses the properties of water, detergents and surface active agents. The paper underlines the importance of the "#B value, critical micelle concentration, solu!ility of surfactants, $rafft and cloud point in conservation. %ashing processes using surface active agents, the connection !etween the chemical structure of surfactants and detergency, the role of soil&dirt anti-redeposition agents, foam, p", washing time and temperature in cleaning are discussed and the composition of solutions for washing historical textiles are given. The paper introduces the dependence of rinsing on the adsorption of surfactant to textiles and reviews the use of vacuum suction in wet cleaning. The efficiency of washing and the effect of washing on fi!res, textiles and dyes is assessed and the review ends with references to !iodegradation of surfactants and a list of selected case studies. Introduction Wet cleaning is a widely used conservation treatment for historical textiles. It is a cleaning method using water as a solvent alone and as a solvent and/or medium for surface active and soil antiredeposition agents and other additives. The use of buffers and agents involving chemical reactions between the dirt and the agent such as se!uestering agents" bleaching agents and en#ymes$" are not included in this review. %efore the &''(s many textile conservators may have agreed with )urian-*ees who said that +dirt is not part of old age+ ,&-. In the last decade of the twentieth century several publications call textile conservators+ attention to the danger of removing valuable curatorial information from historical textiles by wet cleaning" for example .astop and %roo/s ,0" 1-" 2all and %arnett [4], )odds ,3-" %roo/s et al. ,4" 5-" 6ohansen ,7-" 8tauffer ,'- and Windsor ,&(-. 2owever" wet cleaning has many advantages and removing harmful dirt can serve conservation as discussed by Timar-%ala#sy et al. ,&&-. 8oiling on historical textiles )irt or soiling is an undesirable matter adhering to surfaces and influencing their appearance. According to A/ar ,&0-" carpet sweepings contain particles with a diameter from & to over 0( pm" consisting of inorganic materials" cellulose fibres" animal fibres" oils and resinous materials. 9c:innon and 9c;aughlin ,&1- focus on soil+s adherence to fibre. <lothing in contact with human s/in pic/s up greasy human sebum containing about 1&= free fatty acids" 0'= triglycerides fats and oils$" &3= fatty alcohols and cholesterol" 0&= hydrocarbons and 1.1= short chains fats and oils as characteri#ed by >atterson and ?rindstaff ,&@-. These authors also ma/e connections between soil release" soil type and fibres" yarn and fabric geometry. According to >owe [15], the low melting point of sebum 1( A<$ is due to the complex mixture of lipids !uite different from body fat. The strong bonding of fat to polyester fibres has been investigated by Weber et al. ,&4-. The damaging effect of various stains has been discussed by Timar-%ala#sy and .astop ,&5" pp. &35-40- who characteri#e soils according to their potential to cause damage to textiles. Armstrong et al. ,&7- deal with the problem of removing carbon blac/" while <arter ,&'- gives an overview of iron stains on textiles. 6ordan ,0(- reports on the removal of lime plaster from medieval woollen embroidery and 2utchins ,0&- and 2ersh et al. ,00- discuss the effect of deterioration products on

fibres. The ageing process of oil stains on textiles has been described by both Andrasi/ ,01- and 9oreland ,0@- and it has been found that coloured organic substances" such as dyes" in/s and pigments increase the light-sensitivity of fibres. 9icro-organisms" such as bacteria and micro-fungi" cause biological deterioration" characteri#ed by <aneva et al. ,03- and as %allard ,04- describes" the stiffness of synthetic resins on a textile artefact may increase on ageing" thereby inducing mechanical damage in the obBect. >articulate dirts" such as dust" sand" earthy material and corrosion products" may be attracted by the negatively-charged surface of textiles or may bond to the textile by rather wea/ electrical forces" as described by *ice ,05-" According to >atterson and ?rindstaff ,&@-" the removal of such particulate dirt is largely si#e-dependent: particles of (.0 pm or less are almost impossible to remove from textiles by-wet cleaning. ;arge particles up to 3 pm$ may also be difficult to remove. Timar%ala#sy and .astop ,&5" p. &3'- refer to deterioration products of fibres" body oils" perspiration" finishes or adhesives" water stains" dyes and stains originating from fruits and micro-fungi as molecular soiling. 8oiling forming a large mass on textiles includes greasy or oily dirt" proteins or polysaccharides" synthetic adhesives and paints. Three main types of +dirt+ are distinguished by 9atteini et al. ,07- according to their different response to various cleaning methods. )irt has also been characteri#ed according to electrostatic attraction and secondary bonds van der Waals/dispersion" dipole and hydrogen bonds$ by 9oncrieff and Weaver ,0'" pp. &4-0&- and 2ofen/ de ?raaff ,1($. :issa ,1&" p. 17@- formulates this as follows: 'The removal of a soil particle from a su!strate during laundering involves !rea(ing an adhesive !ond !etween the particle and the fi!er. The strength of this !ond, and conse)uently the energy re)uired to detach the particle, depends on the attractive *mainly +an der %aals, forces and the contact area !etween the soil particle and the fi!er surface.' 8aito et al. ,10- correlate the adhesion of oily dirt with washability by applying the surface energy analysis method to the detergency system. 8mith and 8herman ,11- give a detailed review of the effect of fibre surface characteristics and fabric construction on soil release" and distinguish between +micro-occlusion+" in which fine soil particles became entrapped in the small crevices of fibres" and +macro-occlusion+" in which soil particles became entrapped between fibres in the yarn and between yarns in the weave. They found that +micro-occlusion+ has much more influence in the case of natural fibres than for nylon" which has a smooth surface. Advantages and disadvantages of wet cleaning *ice ,1@- emphasi#es that water dissolves most of the yellow and acidic deterioration products of natural fibresC it also acts as a +plastici#er+ for the polymers of fibres" thereby improving the flexibility and softness of the textile. According to Cooke ,13-" water eliminates creases and wrin/les elastic-deformations$ in textiles by relaxing strains in fibres" yarns and fabrics. Dlury;emberg ,14" 15- finds it very important that in a wet state reorientation of a textile+s yarns and fibres is easier and so its original texture and dimensions may be +recovered+. *ice ,17- discusses possible dimensional and colour changes" as well as dye +bleeding+ problems during wet cleaning. As noted by TEmFr-%alF#sy and .astop ,&5" p. &'@-" historical textiles may undergo further deterioration during wet cleaning. Water 9oncrieff and Weaver ,0'" pp. 53-5- characteri#e the properties of water. The fractional solubility parameters ability to form dispersion" dipole and hydrogen secondary bonds$ of water is published by Torracca ,1'-: dispersion forces$ G fd$H&7" dipole bonds$ ) fp$H07 and hydrogen bonds$ W fh$H3@" which indicates its very high polarity. 9any salts" originating from burial conditions for

example" can be dissolved in water" except ferric De1I$ compounds" which are non-water-soluble according to *ice ,05-. >olar organic soils" such as sugars" some types of polysaccharides e.g..gum arable$ and proteins e.g. animal glue$" dissolve in water. 8eth-8mith and Wedge ,@(- report on the removal of animal glue from tapestry fragments. The purity of water used for wet cleaning in conservation is an important factor. *ain water" coming through the atmosphere may form acids with acidic gaseous pollutants and may carry paniculate soils and bacteria. In tap water various compounds dissolved from the ground and from water pipes can be present. The presence of cations" such as calcium <a0I$" magnesium 9g0I$" sodium Ga I $" potassium :I$" manganese 9n0I" ferrous De0I$" and ferric ion De1I$ in a washing solution is usually undesirable. There are three main reasons for this: The cleaning power of the washing solution for soils containing the given ion will be reduced. <ompounds of heavy and transition metals are catalysts for chemical reactions contributing to further deterioration of textiles. <ompounds of these metals may turn into coloured compounds by photo-oxidation or form coloured compounds with other soiling on the textile. The ?uild of <leaners and ;aunderers ,@&- gives an example: the maximum concentration of iron compounds that does not cause obvious harm to textiles is two parts of iron in ten million parts of water. 2owever" in the case of wool the tolerance is lower: anything in excess of one half part per ten million can cause yellowing and discoloration of wool textiles. The presence of metal ions with two or three positive charges prevents the removal of ionic dirt or polar organic compounds because of their attraction for the negatively or partially negatively-charged parts of dirt molecules" thus the +washfastness of the soiling+ is improved" as noted by 2ofen/ de ?raaff ,1(" @0-. To avoid this phenomenon" she advises that the concentration of cations with two or three positive charges must be very low less than &(-3 g-ion/litre$ in solutions used to wash historical textiles. Anions in tap water may also originate from water soluble-compounds salts$ found in the ground" from sulphates 8J@0-$" carbonates (CO1 0-$" hydrogen carbonates 2<J1- $ nitrates (NO1-) and chlorides <l-$. Water hardness is caused by water-soluble compounds of calcium and magnesium. +2ard+ water is the term used to describe water that does not form a lather with soap but instead forms an insoluble precipitate" called +lime-soap+. This whitish scum is formed from calcium and magnesium ions with the anion of the soapC it deposits in the small pores on textile fibres causing an undesirable greying of the fabric. According to Wal/er ,@1-" calcium ions also form salts with anionic surfactants: calcium al/yl sulphonates and sulphates have :rafft points that are generally higher at the temperature used for wet cleaning in textile conservation" hence precipitation of the surfactant onto the textile may occur see below for a discussion of :rafft point$. The calcium salt of sodium lauryl sulphate" for instance" is insoluble below 3( A<. Arai ,@@- studied the effect of the concentration and the /ind of detergent in hard water. A linear relationship between the concentration of detergent and water hardness at maximum oil removal efficiency was found. Diltering" softening" deioni#ation" reverse osmosis and distillation can be applied for purification of tap water. %ede ,@3- suggests that conductivity measurements can be used to monitor the presence of minerals in water. In theory" pure water has a resistance of &7 megohms/cm at 03 A<" and contains (.(07 ppm total dissolved solids. >ure water is considered by some conservators to be too aggressive and thus will dissolve too much soiling e.g. fibre/finish/ degradation products$ and therefore some conservators prefer a purity of & to @ megohms/cm. )istilled and deioni#ed water are aggressive solvents capable of achieving the maximum solubility of a given compound. According to 2eald ,@4-" deioni#ed water can be damaging to historical textiles. The +softening+ of water refers to the process of exchanging the calcium and magnesium ions in +hard+ water for sodium ions. There are two common methods of water softening: ion exchange with ion-exchange resins and formation of non-soluble or soluble compounds of calcium and magnesium with a chemical additive. 8e!uestering agents also referred to as chelating agents and complexbuilders$ form co-ordinate bonds with metal ions to give a complex. >henix and %urnstoc/ ,@5characteri#ed their role in conservation. According to 2ofen/ de ?raaff ,@0" @7- the calcium and

magnesium ions are held strongly in the complexes and therefore they cannot replace the sodium of soap or other washing agents. Adding polyphosphates often results in an al/aline p2 of the washing solution. )i-" and tetrasodium salts of ethvlene diamine tetra-acetic acid .)TA$ are effective se!uestering agents. The complex formation of disodium salt of .)TA with calcium or magnesium$ results in an increase of protons hydrogen/hydroxonium ions$ in the solution due to the exchange of the hydrogen to calcium or magnesium$. As the p2 of the washing solution containing this softening agent will decrease strict control of p2 is re!uired. )etergents" detergency )etergents added to water create washing solutions. Their role is threefold: promoting wetting of the textileC dislodging the dirt and separating it from the fibresC /eeping the dirt in a dispersion and/or emulsion. The definition given by )avidson and 9ilwids/y ,@'" p. &- for a detergent is a formulation comprising essential constituents surface active agents$ and subsidiary constituents builders" boosters" fillers and auxiliaries$. According to Geiditch ,3(" p. '-: '-etergency refers to the process of cleaning the surfaces of a solid material !y means of a li)uid !ath involving a physico-chemical action other than simple solution. .enerally it is considered to !e an unusually enhanced cleaning effect of a li)uid hath caused !y the presence of a special agent, the detergent.' 8urface tension of water and surface active agents Water exhibits surface tension at the li!uid-air interface and interfacial tension at the li!uid-li!uid or li!uid-solid interfaces" according to 9oore ,3&-. This interfacial tension hinders water from penetrating and wetting textiles. In a body of water the electric forces of attraction especially hydrogen bonding$ operate in all directions and each molecule is held in e!uilibrium. At the surface of water however" there are no forces acting from the air side and hence the e!uilibrium is disturbed. The energy accumulated in the surface molecules of water is manifested as surface tension. 8urface tension is recorded as Gewtons per metre and the surface tension of water is very high: 50 mG/m. 8urface active agents surfactants$ reduce the surface tension of water and other li!uids. When added to water" surfactants will more or less cover the surface of the li!uid. They are not as strongly attracted to the inner water molecules as the water molecules were previously. According to both Given ,30- and )urham ,31-" the surface tension of water is reduced to the range of 03-@( mG/m in the presence of a surface active agent. 8urfactants are organic compounds with molecules having a hydrophobic water repelling$ nonpolar tail and a hydrophilic water attracting$ polar head or tail. As the attraction forces hydrogen bonds$ between water molecules are much stronger than those between water and the hydrophobic tail of the surfactant" the water molecules tend to +s!uee#e out+ the hydrophobic tail of the surface active agent. A generally coherent layer of the detergent will cover the surface" so that the non-polar tails are in the air while the hydrophilic head/part of the detergent is attracted and dissolved by the water molecules. As the hydrophobic tails of the detergent molecules are pushed out" the water spreads and wets the surface of the textile. )avidson and 9ilwids/y ,@'- give an overview of surfactants" which are divided into four groups depending on the character of the hydrophilic part: anionic" non-ionic" cationic and amphoteric surfactants. 9embers of the first two groups provide a wide range of washing agents" while cationic or cation active$ surface active agents are applied as optical brighteners" fungicides" softening" antistatic or colour fixing agents. Amphoteric surfactants" containing both acid and basic groups in their molecules" act either as anionics or as non-ionics depending on the p2" and have not gained importance in either industry or textile conservation. <haracteri#ation of surfactants given below is based on publication by 6a/obi and ;dhr ,3@-" ;infield ,33- and 8chic/ ,34-.

Anionic surfactants The hydrophilic heads of anionic surfactants ioni#e to a positively-charged cation" while the residue of the surface active agent becomes a negatively-charged ion anion$. 8oaps are metallic salts of fatty acids with &@-&7 carbon atoms in their hydrophobic tail. They ioni#e in water to a positive metal ion and an anion.

9arseilles soap contains a mixture of sodium and ammonium salt of stearic acid <&5211<JJGa I <&5211<JJG2@$ and was recommended for washing historical textiles in soft water by 2ofen/ de ?raaff ,35-" As outlined above" natural soaps can form a scum lime-soap$ in hard water" thereby reducing or inactivating their detergency and precipitating on fabrics. Gatural soaps can cause al/aline p2 in washing solutions and their cleaning efficiency is not good in cold water. .arly anionic surfactants had a close resemblance to soap. Al/yl sulphates" also /nown as fatty alcohol sulphates DA8$" originally were made from fatty alcohols. %oth primary and secondary al/yl sulphates contain &&-&7 carbon atoms.

8odium and ammonium salts of al/yl sulphates have excellent water-solubility and may form water-soluble salts with the calcium or magnesium ions of hard water" thus they do not form insoluble lime-soap precipitates. Jrvus WA" a surfactant produced by >roctor K ?amble and used widely in Gorth America" is sodium dodecyl/lauryl sulphate. Al/yl ether sulphates A.8$ exhibit uni!ue characteristics" such as very low sensitivity to water hardness" high solubility and storage stability at low temperature in li!uid formulations.

8odium <&0-&@ n-al/yl diethylene glycol ether sulphates" for example" demonstrate increased detergencv performance e.g. on wool$ as the water hardness increases. This is a result of the positive electrolyte effects attributable to calcium/magnesium ions. Wal/er ,@1- found the best anionic detergents for cleaning historical textiles in this group have a chain length of <&0-&3 and 0-1 mols of .J. Al/yl phenol-polyethene-glycol$ sulphates A>>?8$ have rarely been used in conservation" apart from ;evapon %ayer$.

sodium phenol-polyethene-glycol-ether$ sulphate

8odium al/yl or al/ane sulphonates 8A8$ may be linear or have a branched chain:

primary sodium al/yl sulphonate

secondary sodium al/yl sulphonate &(-&7 carbon atoms in

8traight and branched-chain al/yl aryl sulphonates AA8$ contain their al/yl chain:

branched chain al/yl aryl sulphonate The L-olefin sulphonates reaction with water. AJ8$ also contain hydroxy-al/ane sulphonates as a result of partial

L -olefin sulphonates

hydroxy-al/anesulphonates

According to 2ofen/ de ?raaff ,@7-" L -olefin sulphonates are well /nown to conservators for their property of being less irritating to s/in and having little sensitivity to water hardness. Another important class of anionic surfactants is the a-sulpho fatty acid esters 8DA.$" particularly the methyl derivatives.

?ood detergencv performance is attained only with products having a rather long hydrophobic part. Jne of the interesting detergencv properties of a-sulpho fatty acid methylesters is their exceptional dispersion power with respect to lime soap. Datty acid methyl taurides" such as 2ostapon T 2oechst$ are /nown for their excellent foaming properties.

sodium oleic methyl tauride 8traight chain linear$ and branched al/ylben#ene sulphonates A%8" ;A8$" exist. Mntil the mid&'4(s" this was the largest class of the synthetic surfactant and was most prominently represented by tetrapropyleneben#ene-sulphonate T>8$:

;A8 has very high foaming abilityC however" it is sensitive to water hardness: the detergencv power of ;A8 diminishes as the hardness of water increases. 8mith et al. ,37- attribute this sensitivity to the formation of <a ;A8$0 on addition of calcium ions to ;A8. Initially the micelles can solubili#e the <a ;A8$0 but" in the presence of a higher concentration of calcium" the micelles capacity becomes exhausted. Gatural anionic surfactants are not widely used in conservation cleaning. 2owever" the search for a biodegradable surfactant to replace 8ynperonic G" manufactured by I<I see below$" led to an investigation of the seaweed funori" a marine algae of the ?loiopeltis genus" by Ta/ami ,3'-. The main component of the mucilage extracted from the dried sheets is a partially sulphated and methylated polysaccharide" named funoran. Msing a torsion balance to measure the surface tension of eleven different concentrations of funori (.& to &.3= v/v$ at 0( N<" she found that it decreases the surface tension of water from the 51 mG/m to 3@ mG/m" which means that it has some surface activity but less than most synthetic surfactants 0@-@( mG/m$. Ta/ami+s initial findings indicate that a (.&= funori anionic surfactant solution may be suitable for washing historical textiles" subBect to further tests. Gon-ionic surfactants The term +non-ionic surfactant+ chiefly refers to polyoxyethylene and polyoxypropylene derivatives" but other surfactants are also included in this category" such as anhydrohexitol derivatives" sugar esters" fatty al/anol amides and fatty amine oxides. Gon-ionic surface active agents do not ioni#e in water. The proportion of hydrophilic parts to the hydrophohic tails is different from that of anionic surfactants: in non-ionic surfactants the polar part/tail can be as large or even larger than the nonpolar tail. .mbree ,4(- mentions the use of soap bar/ soap wort" 8aponana$ for washing and <ains ,4&records that the soapwort plant was called +radicula+ by the ancient ?ree/s and *omans" who used it for cleaning wool. 8hashoua ,40- reports on using saponin for washing sil/ and <#erwins/e ,41carried out experiments with 8aponin )A% ' obtained from the bar/ of the <hilenian OuillaBa tree OuillaBa saponaria 9olina$ and of the roots of saponin 8aponana officinalis ;$. This is a non-ionic substance" which decreases the surface tension of water from 51 mG/m to 0( mG/m at 0( N< in a concentration of &.3 g/litre. TsuBii ,4@- classifies saponin as two types" steroid and triterpenoid" in which hydrophilic saccharides glucose" galactose" rhamnose" xylose" pentose" etc.$ are attached to hydrophobic steroids and triterpene. 9ost synthetic non-ionic surfactants used in conservation are of the ethylene oxide class. If the polymeri#ation of ethylene oxide is carried out in the presence of organic compounds containing easily exchangeable hydrogen e.g. fatty alcohol$ the product will be an ethylene oxide adduct. The proportion/si#e of the hydrophilic and hydrophobic part can be +tailored+ to the planned role of the surfactant in washing. Wash effectiveness shows an initial increase with an increasing degree of ethoxylation" but a point is then reached after which the wash effectiveness declines mar/edly.

)illan ,43- found that narrow-range& ethoxylates contain less unreacted fatty alcohol and other water insoluble species and they are capable of forming a!ueous solutions with much lower cloud points than their broad-range counterparts. The general formula of al/ylphenol polyglycol ethers A>.J$ is as follows:

These surfactants" which have exceptional detergency properties and" in particular" oil and fat removal characteristics" show low biodegradibility for a discussion of biodegradability" see below$ 8ynperonic G is an ethylene oxide adduct .J H 7$ with nonylphenol. 2;% The detergency of a surfactant depends greatly on the balance %$ of the molecular weight of the hydrophobic 2$ portion to that of the hydrophilic lipophylic" ;$ portion. >orter ,44- asserts that calculation of the 2;% number was first proposed in &'@'. 2;% H = of the hydrophilic group molar$ divided by 3. The maximum 2;% number is 0( and represents a completely water-soluble surfactant" while an 2;% of #ero represents a completely water-insoluble product. %oring and .wer ,45- ma/e a connection between 2;% value and application: Table & <onnection between 2;% values" appearance on adding surfactant to water after >orter ,44- and %oring and .wer ,45-$

It should be noted that an increase in temperature will bring about a phase inversion from an oil in water JAP$ to a water in oil W/J$ emulsion due to the non-ionic surfactant becoming less watersoluble as the temperature increases. )elcroix and %ureau ,47- suggest that for non-ionic surfactants" it is better to use a mixture of surfactants with different 2;% values" giving the desired proportions" than to use a single one that has the re!uired 2;% value. A strongly hydrophobic surfactant has a low 2;%" usually less than &(. A highly hydrophilic surfactant has a value higher than &(. Dor example" polyethylene nonylphenols have an 2;% of about &1 and sodium lauryl sulphate has an 2;% value of approximately @. According to :ravet# via a personal communication with Wal/er ,@1-" solutions of linear primary alcohol ethoxylates <&0-&3" .J 1 to @ mols" blended and mixed with varying 2;% values are efficient for washing historical textiles. 8urfactants of 2;% &( to &0 are effective for oily soil and those with a higher 2;%" &1 to &3" for particulate soil. Wal/er recommends a two- or three-step washing process" starting with a lower and ending with a higher 2;% surfactant.

Wetting properties of surfactants In the presence of a surface active agent" the interfacial tension between water and textile is reduced and the textile is wetted. Parious surface active agents show various wetting properties" depending on their chemical and stereo-chemical structure e.g. the length of hydrophobic and hydrophilic parts" straight or branched chains and the presence of an aromatic ring in the molecule$. The wetting property of a surfactant is characteri#ed by the measurement of the +rim angle+ and +contact angle+" described by %igler ,4'-. The +rim angle+ is the tangent of the angle between the solid and the li!uid surface measured in the air. It increases as the wetting increases. Ward and %enerito ,5(- define +contact angle+ as the angle between the solid surface and the tangent of the li!uid surface as it approaches the solid" the angle being measured in the li!uid. The contact angle decreases as the wetting increases.
&

When reacting detergent-range primary alcohols <&0-&@$ with ethylene oxide and achieving a narrow distribution of .J moles. The rolling-up process by surfactants in the case of li!uid dirt" such as oil" can be characteri#ed so that the fibre surface is wetted by the oil in the starting state and then it will be wetted by the a!ueous phase. This process" which results in cleaning" can be followed by the decrease of the rim angle and an increase of the contact angle between the oil stain and fibre while it is rolled up by a surfactant solution" as depicted by ;ange [71, p. &37-. At the beginning of the rolling-up process the oil is a flat stain on the surface of the textile. As it is lifted up step by step it curls in a ball-shaped oil particle and separates from the surface of the fabric. <ritical micelle concentration The total number of surfactant molecules that enter the li!uid surface is determined by a balance of forces: between those s!uee#ing out the hydrophobic tails and the repelling forces between li/echarged parts of the surfactant molecules. When a surface active agent is added to water" so that its concentration gradually increases" the number of the surfactant ions at the surface increases up to a certain critical concentration of the detergent. The excess surfactant molecules i.e. those added since the critical concentration was reached$ cannot access the surface or stay individually in solution but form micelles within the body of the li!uid. 2ence the term critical micelle concentration cmc$. 2utchinson and 8hinoda ,50" p. &1- define micelle as +hydrated surfactant in li!uid state+. 8ince the micelles are small compared with the wavelength of light" the solution is transparent. According to the above authors" micelles have a solubili#ation power: when the surfactant solution is above its cmc" the solubility of a third additive is mar/edly greater than in pure water. Went# ,51- also attributes the main mechanism of soil removal in a!ueous systems to this solubili#ation" by stating that non-polar substances are solubilized in the interior of the micelles. 8/agerlind ,5@- published an illustrative figure showing that surfactant molecules are present in single form below" and in micelle form above cmc. 9icelles are aggregates of a number of surfactants. The hydrophobic tails of the surfactant molecules tend to cluster so that they are isolated from the waterC in other words" the water molecules s!uee#e out the non-polar tails of the detergent molecules. The hydrophilic parts of the surfactant align themselves facing the water. 9any suggested configurations for micelles have been suggested" such as spherical" ellipsoid" lamellar and cylindricalC the micelle configuration is thought to depend on the chemical composition and stereo-chemical structure of the surfactant. The micelles themselves are stable entitiesC however" they continually brea/ up and reform in a process of e!uilibrium. With anionic surfactants the outer layer of the micelle is negatively-charged" with non-ionics" the micelles have no charge. According to )elcroix and %ureau ,47-" the number

of molecules in a micelle at room temperature is @(-@'' for a non-ionic surfactant and 0(-1(( for an anionic one. As mentioned by Taylor ,53-" the cmc varies mar/edly according to the character of the surfactant as it is affected by temperature. At low concentrations the amount of micelle formation is negligible and" at higher concentrations" the point of e!uilibrium is to a very great extent independent of the total concentration. The reverse applies to surface tension: at low surfactant concentrations the reduction in surface tension is dramatic" but it does not change above the critical micelle concentration. 2ofen/ de ?raaff ,1(- remar/s that the effectiveness of a washing agent increases up to the critical micelle concentration but decreases after cmc has been reached. ;ange ,5&" p. &51- distinguishes between the mechanism of single surfactant molecules and micelles in cleaning. 2e explains that the increase of cleaning efficiency up to the cmc is due to adsorption of the single surfactant molecules onto the dirt. Thus" solubili#ation of the dispersed dirt is a purely micellar phenomenon. It therefore does not occur unless the concentration is higher than the cmc. The actual mechanism depends both on the surfactant and the type of soil. It seems to be a general experience that a strong increase in cleaning efficiency occurs up to the cmc and only a very slight increase above the cmc. The critical micelle concentration of any one class of surfactant is reduced as the si#e of the hydrophobic tail increases" or the hydrophilic part decreases in si#e. The closer the polar group to the centre of the hydrophobic tail in secondary al/yl sulphates/sulphonates$" the higher the cmc. The presence of more ionic groups in one surfactant molecule also causes an increase in cmc. The cmc also depends on the cation of the surfactant. It reduces cmc with decreasing attraction forces between the detergent ion and the cation: the reduction in cmc is smaller with sodium than with potassium. According to 6uhas# and ;el/esne .ros ,54" pp &04-17-" with non-ionic surfactants the cmc increases as the hydrophilic part .J$ becomes larger. Drom these observations it is clear that non-ionics produce lower surface tensions than anionics at e!uivalent concentrations. Also" at comparable hydrophobic chain si#e" non-ionics form micelles more readilyC this is probably because" without an ionic charge" there is no barrier to aggregation" as noted by Taylor ,53" pp. &(-&&-. Jne of the advantages of using non-ionic surfactants is that the critical micelle concentration is very low" in the order of (.(3-(.3 g/litre in comparison to anionic ones with a cmc of (.1-1 g/litre" thus" the amount of surfactant re!uired is reduced" thereby increasing li!uor clarity and rinsability. According to 6uhas# and ;el/esne .ros ,54" p. &17-" in a!ueous solutions the cmc of anionic surfactants is reduced in the presence of salts of the surfactant+s cation. In addition" the repelling forces between the polar parts of non-ionics are reduced by certain cations. This may explain why se!uestering agents providing cations on ioni#ing reduce the cmc of the detergent. )irt containing a similar cation to those of the anionic surfactant may have a similar effect" that is such soiling may reduce the cmc of anionic surfactants. Thus" when wet cleaning archaeological textiles contaminated with sodium compounds" a lower concentration of an anionic washing agent may be as effective as one of its cmc. 8olubility of surfactants" :rafft point and cloud point The solubility of surfactants depends largely on the length and proportion of their hydrophobic and hydrophilic parts 2;%$" as well as the number and position of ionic or polar groups. According to )avidson and 9ilwids/y ,@'" p. &(-" lauryl alcohol reacted with ten molecules of ethvlene oxide is completely water-soluble and a good detergent" while one with less that five molecules of ethylene oxide would be insoluble. Temperature is another factor that determines the solubility of surfactants. %elow a certain temperature" the apparent solubility of an anionic surfactant drops dramatically. In contrast" the solubility of non-ionic surfactants drops considerably above a certain temperature. The temperature at which the solubility of a surfactant decreases sharply and the undissolved detergent molecules appear in the form of a whitish cloud" is called the +cloud point+. In a +cloudy+ solution only the

soluble invisible$ portion of the surfactant carries out its surface activity. Qi/a ,55" p. 05/10@- gives the following definition: +nominal cloud point: the temperature at which a cloud of insoluble surfactant first begins to form in a &= a!ueous solution of the surface active agent+. The solubility of anionic surfactants depends basically on the length of the hydrophobic chain. If there are fewer than &( carbon atoms in the non-polar chain" the detergent may be too soluble to form micelles suitable for soil removal. If it contains more than &7 carbon atoms" the anionic surfactant molecule is too large to be soluble at reasonable wor/ing temperatures. A surfactant with unsaturated hydrophobic chains is more soluble than a similar saturated chain compound. *ice ,57gives an example: a sodium oleate surfactant <&5211i<JJGa$ with an unsaturated chain dissolves in cooler water than its saturated counterpart" sodium stearate surfactant <&5213<JJGa$. The solubility of anionic surfactants increases as the temperature rises and hence cloudy solutions clear as their temperature is increased. There is a critical solubility temperature" called +:rafft point+: above this temperature the solubility of the anionic surfactant increases dramatically with increasing temperature. 9icelles cannot form below :rafft point. Wal/er ,@1- provides an example: the :rafft point of 8)8 is about &( A<. At &0 A< its solubility is (.(0=. This increases to (.0= at &4 A< and to 1= at &5 A<. 2utchinson and 8hinoda ,50- formulate that at low temperatures the precipitate of anionic surfactants will be in e!uilibrium with the saturated solution of singly dispersed surfactant molecules. In contrast" at high temperatures the precipitate becomes transformed to a li!uid state. If the temperature cannot be varied under practice conditions" another e!uivalent effect may be to change the molecular structure of the surfactant or to add a third component in order to depress the :rafft point. %ranching or unsaturation in a hydrocarbon chain causes a mar/ed reduction of the :rafft point. In contrast" the cloud point temperature of non-ionic surfactants can be rather low and the +cloud+ appears above the cloud point temperature. The solubility of non-ionics decreases as temperature rises. )ifferent theories are advanced to explain this particular cloud point phenomenon" described by Qi/a ,55- in a paper in &'4'. Jne states that the hydrogen bonds" formed between the polyethylene oxide part of the detergent and the water molecules" brea/ with increasing temperatures. The higher the temperature the more hydrogen bonds brea/. As a result" the surfactant becomes insoluble. Another theory claims that with increasing temperature the micelles of the nonionic surfactant grow larger" to the point where they can actually be seen in the form of a +cloud+. Water hardness greatly influences the solubility of detergents. Those anionics that form non-watersoluble compounds with calcium or magnesium such as soap" al/yl ben#ene sulphonates or secondary al/yl sulphonates$ have a much lower cloud point than other anionics. No !io i"s are not usually sensitive to hard water and it is the presence of electrolytes that lowers their cloud point. 6a/obi and ;ohr ,3@" p. 35- note that in the presence of pure non-ionic surfactants the cloud point can be reduced greatly by the addition of several grams of electrolytes. Washing process with surface active agents In general" the wash effectiveness of anionics increases with increasing chain length" as described by 6a/obi and ;ohr ,3@" p. @0-. Dor example" surfactants bearing n-al/yl groups show a linear relationship between the number of carbon atoms in the surfactant molecule and the logarithm of the amount of surfactant adsorbed on activated carbon or /aolin. The structure of the hydrophobic residue also has a significant effect on surfactant properties. 8urfactants with little branching i their al/yl chains generally show good wash effectiveness but relatively poor wetting characteristics" whereas more highly branched surfactants are good wetting agents but have unsatisfactory detergency. Dor compounds containing an e!ual number of carbon atoms in their hydrophobic residues" wetting power increases mar/edly as the hydrophilic groups move to the centre of the chain or as branching increases" but a simultaneous decrease in adsorption and washing power occurs.

The micelles formed around the cmc provide reserves of surfactant molecules" which are not only available for instant mobili#ation" but also have the power to solubili#e substances" such as fat" which do not dissolve in water. Taylor ,53" p. 5- describes fat as being +solubili#ed+ within the hydrophobic interior of the micelle. In wet cleaning textiles" a surfactant solution is applied and soil removal is promoted by careful agitation. According to :issa ,5'" p. 541-: 'The process of washing *soil release, consists of three consecutive stages/ an induction stage, during which water diffuses into the soiled textile !ut soil release is slow0 a rapid soil release stage, during which 'rolling up' and dislodgement of soil and water diffusion are rapid0 and a final stage, during which soil retention in the textile remains essentially constant'. The hydrophobic tail of a surfactant penetrates hydrophobic soiling" while the polar part of a nonionic penetrates polar soiling. Through the penetration of surfactant molecules" the soiling on a textile surface is dislodged deflocculated$ into small particles. The four stages of this process are depicted in an illustration in a paper by 9oncrieff et al. ,0'" p. 7@-. Anionic detergents re!uire a long time to penetrate negatively-charged soils" such as clay or carbon blac/" due to the mutually repelling forces present. )iffusion of the surfactant into the textile is hindered by the repelling action between the anionic surfactant and textile" which also has partial negative charges on its surface due to the polar groups of the fibre polymers. Anionic detergents dissolve soiling particles of non-polar character in the micelles and they bond to polar soils by secondary dipole and hydrogen bonds with their polar heads. In the case of polar soils" a second layer of surfactant molecules Boins the first layer and thereby a double anionic surfactant layer prevents polar soiling particles from aggregation. According to Qi/a ,55-" non-ionic surfactants are e!ually good at penetrating both non-polar and polar soils due to the e!ual length of non-polar and polar parts and the absence of any charge. Gonionic surfactants bond to polar soils by dipole and hydrogen secondary bonds with their polar parts and by van der Waals bonds to non-polar soiling with their non-polar parts. Gon-ionics penetrate soiling and textile !uite !uic/ly" especially if the hydrophobic part is of a straight chain type. Gon-ionic detergents with &0-&@ carbon atoms in their al/yl chain and &( .J groups are excellent at penetration" but octyl- to dodecylphenol detergents with &( .J groups are also very effective at soil penetration. Applying a mixture of anionic and non-ionic surfactants in the same washing solution has the advantage of forcing off soiling by the anionic surfactant and at the same time penetrating various soiling by the non-ionic surfactant. %erol 57@ %erol Gobel$" for example" is a mixture of an anionic al/yl aryl sulphonate$ with a non-ionic fatty alcohol ethoxylate$ surfactant. ?entle and 9uller ,7(combined anionic and non-ionic surfactants in the same washing solution and achieved a good result in terms of cleanness. ;ewis ,7& - experimented by mixing 8ynperonic A3 non-ionic and 8)8 anionic surfactants and found its efficiency better than either single surfactant for washing wool. 8tauffer ,70- provided the author with leaflets on two mixed surfactants used by ?erman textile conservators: Invadin ;MG <iba-?eigy$ and :ieralon J;% %A8D$. <hemical structure of surfactants and detergency 8tupel ,716 lists surfactants according to their increasing cleaning power: primary fatty alcohol sulphate RSal/yl polyglycol ether RSal/yl aryl sulphonate dodecilben#ene sulphonate$ R Ssecondary fatty alcohol sulphate tridecylsulphate$ RSfatty acid condensation product oleyl methyl taurine$ RSal/yl sulphonate. 6ones ,7@- reported on variables affecting efficiency of amonic surfactants in soil removal: straight al/yl chains on ben#ene sulphonates are superior to branched chainsC effective detergency of ben#ene sulphonates begins with an al/yl chain length of &( carbon atoms and improves to a

maximum at &@-&4 atomsC p-al/ylben#ene sulphonates are superior to o-al/yl compoundsC straightchain carboxylates and sulphonates have similar detergent activity. 2arris ,73- and 8chonfeldt ,74- investigated surfactant effects and summari#ed that optimum soil removal activity for non-ionic surfactants is produced by condensing ethylene oxide with a normal straight chain aliphatic hydroxy compound with &0-&@ carbon atoms in the chain and about &( ethylene oxide units. They found that branched al/yl chains give less efficient detergent action than straight chains and that aromatic derivatives" such as octyl- and dodecylphenol" provide effective non-ionic surfactants when condensed with about &( mols of ethylene oxide. Gon-ionic surfactants soluble in dilute solution at room temperature can become insoluble at higher temperatures and their detergent action is optimi#ed close to this condition" while low levels of nonionic surfactants form micelles in water so that the amount of these compounds needed for optimum soil removal is less than that of anionic surfactants. The authors noted that effective soil solubili#ation shown by non-ionic surfactants is an additional removal mechanism not available with ionic materials and that non-ionic and anionic surfactants combined in detergent mixtures can give more effective soil removal than either surfactant alone. When evaluating surfactant groups according to their cleaning power one has to bear in mind that the actual effect of the surfactant chosen depends on the individual surfactant selected from a particular group" the type of textile and soiling and other components of the washmg solution as well as the washing temperature" p2" mechanical action and the duration of washing. 8oil/dirt redeposition and soil/dirt anti-redeposition agents In the last stage of washing the role of the surfactant is to /eep the dislodged soil particles in a stable suspension" dispersion or emulsion and prevent soil redeposition on the textile. According to *ice ,05-" an average strongly-adhered" plate-li/e clay soil particle is about (.& Tm in diameter. <arbon deposits that exhibit strong greying power appear to be about (.(3 Tm in diameter. 2aving been bro/en down by the surfactant" the soils turn into much smaller particles" which can deposit in the surface crevices of vegetable fibres" at the Bunctures of animal fibres with scales and in the complex surface structure of some synthetics. 8uch fine" redeposited soiling results in a dull" uniformly grey appearance" which is very difficult to remove. *ice ,05" p. &1- discusses the problem in detail. 2ofen/ de ?raaff ,1(- characteri#es washing as a process of e!uilibrium where the amount of soil +rolled up+ by the detergent is in e!uilibrium with the amount of redeposited soil:

The e!uilibrium is shifted in the direction of the upper arrow if dirt is held strongly in the washing solution. *edeposition of soiling can be prevented if a washing solution loaded with dirt is replaced before the e!uilibrium is shifted towards the lower arrow. 2ence" li/e-charged +soil-surfactant micelles+ repel each other and are repelled by the textile" anionics usually act well in preventing soil-redeposition. The dirt-carrying properties of anionic surfactants are usually excellent if the surfactant is present above its cmc. Gon-ionics solubili#e or retain mixed non-polar and polar soils i.e. greasy dirt$ in a stable dispersion" whether or not they are present below or above their cmc. 6uhFs# and ;el/esne .ros ,54" p. 01'- state that the use of a mixture of anionic and non-ionic detergents in the same washing solution has advantages for soil-carrying. Dor example" the anionic detergent sulpho-succinate does not have very good washing properties but is excellent in soilcarryingC this applies also to anionic fatty acid-al/anol-amides" which also promote the stability of foams.

>atterson and ?nndstaff ,&@- list special soil anti-redeposition agents" such as polyvinyl alcohol" polyethylene-glycol" polyvinyl pyrrohdone as well as sodium carboxy methylcellulose hydrophilic polymers. The most common soil carrier used in washing historical textiles is the carboxy methylcellulose <9<$ and its sodium salt (#C$C or Ga<9<$. A paper by ;ange [71, p. &33refers to several theories about the mechanism of inhibiting soil redeposition by <9< and 8<9<" such as reinforced electrical repulsion" competitive adsorption" protective colloid action and steric protection. The usual recommended concentration of 8<9< in a washing solution is (.(&= of the !uantity of the surfactant. <omplete dissolution of 8<9< re!uires a rather long time about 0@ hours$. 8mith and ;amb ,75- recommend 8<9< with a small degree of polymeri#ation )> H 0((-3(($ and with a low degree of substitution )8 H (.4-(.7$ for soil-carrying purposes. -a/obi and ;ohr ,3@" p. '(mention the use of carboxymethyl starch <98$" as well as non-ionic cellulose ethers. The cellulose-based soil anti-redeposition agents are particularly effective with cellulose-containing fibres. These agents form a barrier layer on the surfaces of cellulosic fibres. The advantage in soilcarrying is a disadvantage in separating cellulose-based soil anti-redeposition agents from cellulosic textiles" which re!uire repeated rinsing at rather high temperatures. 8e!uestering agents also act as soil carriers" partly by forming complexes with the metal ions of dirts" partly by their dispersing" emulsifying and stabili#ing properties" which are limited in comparison to surfactants. <omposition of washing solutions for historical textiles and methods of washing <ommercial washing powders and li!uids are unsuitable for cleaning historical textiles due to the presence of many unwanted additives" such as complex builders" optical brighteners" en#ymes" corrosion and foam inhibitors" bleaching agents" stabili#ing agents" dyestuffs" fillers and perfumes. These are described in papers by ;ehmann ,77- and 2ofen/ de ?raaff ,35-. In an unpublished report Wyeth ,7'- lists specific surfactant properties desirable for a conservation cleaning agent: effective lowering of interfacial tensionC good wetting powerC low cmcC high solubility at low temperatures i.e. low :rafft/cloud point$C efficiency at neutral p2 rangeC low sensitivity to water hardnessC good detergencyC soil anti-redeposition capabilitiesC rinsabilityC neutral odourC favourable handling characteristicsC acceptable biodegradabilityC storage stabilityC reasonable price and availability in small !uantities. 2ofen/ de ?raaff ,@7- recommends various formulations for washing historical textiles ta/ing into account the fibres of the textile" nature of the dirt" !uality of the water and the foaming property of the detergent. <ollins ,'(- advocates non-ionics and natural soap for washing undyed cotton and linen. 8hashoua ,40- describes a so-called +8tandard Washing 8olution+ used for experimental cleaning purposes. %oring and .wer ,45- surveyed wet cleaning and found that anionic surfactants were used in a concentration of (.0-(.3= and non-ionics in a concentration of (.(3-(.(0= at 0(-05 A<. Dor washing" the use of deioni#ed water and for rinsing the use of tap water was reported. 2ogberg ,'&- reports an opposite approach" using tap water for washing and deioni#ed water for rinsing. Washing solutions for historical textiles normally contain a surfactant" either an anionic surfactant in a concentration of (.3 to &.( g/litre" or (.&-(.3 g/litre of a non-ionic surfactant as well as distilled" deioni#ed" deminerali#ed or soft water. ?eneral formulations for detergents are summari#ed by )aniels and 8hashoua ,'0$. The <anadian <onservation Institute have produced two notes ,'1- and a report ,'@- on the wet cleaning of textiles" recommending a (.3= concentration of anionic detergent for cleaning textiles in cultural heritage collections. In general" non-ionic and anionic surfactants combined in a single detergent mixture result in more effective soil removal than any single surfactant alone" especially in the conditions appropriate for treating historical textiles" according to >atterson and ?nndstaff [14]% What is probably the first published report on using both /ind of detergents for cleaning a piece of historical textile dates from &'44" when *ice ,'3- used a fatty alcohol sulphonate anionic detergent in the first wash bath and an

ethylene oxide condensate non-ionic in the second. <ox et al. ,'4- investigated the interaction between ;A8 and non-ionic surfactants and found that the addition of low levels of a lauryl rangehigh .J non-ionic surfactant significantly lowers cmc and causes the formation of micelles containing predominantly non-ionic molecules. Gon-ionic surfactant enhances ;A8 hard water performance by preventing the loss of ;A8 via <a ;A8$0 precipitation. The non-ionic surfactant acts as a micelle promotion agent" while ;A8 remains responsible for surface and mterfacial properties. )avis ,'5" pp. &3'-41- reports on using a 0 g/litre solution of 8ynperonic G non-ionic surfactant mixed with a solution of (.3 g/litre sodium dodecyl sulphate" anionic surfactant. Dor washing a severely soiled curtain she used a solution of (.3 g/litre 8ynperonic G" (.3 g/litre sodium dodecyl sulphate and 0.(( g/litre 8<9<. 2ofen/ de ?raaff ,'7- lists the following additives as sometimes also being used in washing solutionsC a soil-carrier of sodium carboxy methyl cellulose 8<9<$ in a usual concentration of (.(3-(.& g/litreC a se!uestering agent" which can be added to soften water and/or to remove heavy soils containing metals" in a usual concentration of (.3 to 0.( g/litre and a buffer" added to maintain the p2 of the washing solution when treating highly acidic textiles. In washing solutions for historical textiles the use of distilled" deminerali#ed" deioni#ed or soft water is recommended. ?iuntini and %ede 1223 used deioni#ed water without any detergent for washing a group of >aracas mantles" as did :aBitani ,&((- when wet cleaning a 9unghal court robe. )istilled water alone was recommended for wet cleaning of archaeological textiles by Qongyou ,&(&&. A (.0= solution of 8ynperonic G non-ionic surfactant containing (.((3= <9< was used by :iefer ,&(0- for cleaning a shattered sil/ brocade. <ussel ,&(1- compared the %ritish and the Drench methods of wet cleaning and noted that there is little difference between them" although in the M: 8ynperonic (&C&), and in Drance Tinovetine <iba-?eigy$" are the preferred surfactants. A detergent formula containing 8ynperonic G non-ionic surfactant" #C$# and sodium tripolyphosphate was published by ?lover ,&(@- in a report on the textile conservation methods in north-western .ngland. %urgess ,&(3- suggests that textiles made of cellulosic fibres should be washed and rinsed in a solution containing 0( to 0(( ppm of magnesium sulphate 9g8J@$ dissolved in distilled water. This reduces the loss of calcium and magnesium from the cellulose hemicellulose and pectin$ and thereby improves the stability of the polymers of the vegetable fibres. In a personal communication" 2ofen/ de ?raaff ,&(4- felt that this method should be subBect to further debate" as the presence of calcium and magnesium ions in the wash bath hinders soil removal and" unli/e paper" the !uantity of calcium and magnesium in cellulosic fibres is very low. 8henai ,&(5- recommends using nonionic" rather than anionic" surfactants to wash wool because they have a lac/ of substantivity to wool. )elcroix ,&(7- gives a sophisticated mathematical process for determining the ideal concentration of a surfactant used for wet cleaning historical textiles for the $ai so <hevalier in Aubusson" Drance. Washing temperature The washing temperature has a great influence on the solubility i.e. cloud point$ of surfactants. The solubility of anionics increases as the temperature rises. 8urfactants" with long polar chains" for example non-ionics" dissolve readily in cold water. The solubility of non-ionics decreases as the temperature rises. Al/yl sulphate anionics with &@-&4 carbon atoms in their chain are excellent washing agents with good micelle formation and soil dispersing properties. Their use re!uires the temperature of the washing solution to be above @( N< to reach the critical micelle concentration. This temperature is too high for textile conservation purposes because of the damaging effect of swelling" shrin/ing" felting or hydrolysis of degraded fibres" as well as bleeding of dyes or dissolution of too many degradation products. Thus" anionic detergents are often used in conservation at lower temperatures" i.e. below their cmc. According to 9orris and >rato ,&('-" the effect of the washing temperature on the removal of particulate and oily soiling depends on the fibre type too. ?enerally from both cotton and polyester

fabric the dirt removal improves as washing temperatures increase from &( to 3@ A<. *emoval of non-polar oily soil from polyester fabric was a notable exception" where soil removal was inversely related to wash temperature. 9yers ,&&(- distinguishes between wet cleaning and laundering" stating that the latter term refers to cleaning at high temperatures. Washing time To prevent too much swelling or hydrolysis of degraded fibres" the duration of washing of historical textiles is normally reduced as much as possible. The use of a suction table in wet cleaning can reduce the time available for fibre swelling. Jn the other hand" according to the three consecutive stages of washing induction time" rapid soil release stage and final stage$" it is not advisable to stop washing before the rapid soil release stage is reached. The induction time of washing is usually shorter with non-ionic surfactants than with anionics due to the lac/ of repelling ionic forces between the textile" soil and surfactant. Gaturally" the induction time depends on the fibres" the thic/ness and structure of the textile" the hydrophobic property of the soils" the temperature of the washing process and the components of the washing solution. <omplete wetting can be achieved in minutes or may ta/e hours" depending on the above factors. In wet cleaning of historical textiles the rapid soil removal period should start and reach e!uilibrium within a reasonable time. The washing process for historical textiles should stop before the end of the rapid soil release stage in order to prevent soil redeposition" as mentioned above with the +e!uilibrium process theory+ of washing. If a single washing solution is insufficient to achieve the re!uired soil removal" the use of two" or more" washing solutions is recommended instead of soa/ing the textile longer in the same bath. With a second or subse!uent bath the rapid soil release stage starts again" and the ris/ of dirt redeposition is therefore reduced. When analysing the answers to the !uestionnaire +Jperation Wetclean+" 2owell and Darnsworth ,&&&" p. 443 concluded that +rinsing times are longer than wash times" wool tends to be soa/ed before washing but sil/ does not" the longest treatment time tends to fit into a wor/ing day" although some conservators were doing very long days.+ The p2 of the washing solution Anionic surfactants re!uire complete io izatio for optimum washing efficiency. Anionics in the form of sodium salt ioni#e better in al/aline conditions than in acid ones. According to 2ofen/ de ?raaff ,@7-" fatty acid methyl ester a-sulphonates are said to be exceptions as they are stable between p2 1 and p2 &(" which ma/es them excellent for cleaning textiles that have become acidic. 8e!uestering agents can act as buffers in a washing solution as they often provide mildly al/aline conditions which promote ioni#ation of anionic surfactants. The degree of ioni#ation depends on the presence of anions in the washing solution e.g. hydrogen carbonate ions$" which results in wea/ly acidic solutions" as well as the counter-ions of anionics e.g. sodium ions$" which result in strongly basic solutions. Thus" the combined use of se!uestering agents with anionic surfactants may result in a wash solution of al/aline p2. If the fibres and dyes are not sensitive to al/aline conditions" there are several advantages to using a washing solution with a mildly al/aline p2 for cleaning nondegraded and non-al/ali-sensitive textiles. These advantages include: improving the cleaning power of the anionic surfactantC brea/ing down fatty soils by saponificationC stabili#ing anionic surfactants and neutrali#ing acids released into the wash bath from the textile and soiling. Gon-ionic detergents do not cause a change in the p2 of washing solutions because they do not ioni#e. They are usually effective in acid conditions. The p2 of the washing and rinsing$ solutions will change throughout a wet cleaning process. <artwright and <olombini ,&&0- emphasi#e the importance of monitoring the p2 of washing solutions throughout every stage of the washing process.

The role of lather foam$ in washing The lathering foaming$ properties of a surfactant can be characteri#ed by the volume of foam produced from a unit volume of washing agent prepared in standard conditions. Doams are dispersions of air bubbles in water" where the li!uid is deformed into thin films. These films of water separate the air bubbles. Dine solid particles from the washing solution float into the foam. The relationship between the cleaning power of surfactants and their foaming properties is not closeC however" surfactant foam decreases the amount of dispersed soil in the washing solution by holding soil in the foam and thereby inhibits soil redeposition. The application of foam to the surface of textiles has the advantage of +drawing up& the soil into the foam without lengthy soa/ing of the textile in the washing solution. 2owever" this cleaning method of using foam alone has drawbac/s: if too much foam is used it can be difficult to rinse out the detergent completely. 6uhas# and ;el/esne .ros ,54" pp. 00(-4- list surfactants with good foaming properties: fatty acid soaps and primary al/yl sulphates with &0-&@ carbons containing above '(= sulphate groups" sodium salts of fatty acid-methyl-taurides e.g. 2ostapon T$ and sodium al/yl ben#ene-sulphonates provide stable foam i.e. the foam bubbles do not collapse over time$. Gon-ionic surfactants except saponin$ provide much less foam than anionics. Adsorption of surfactants to textiles and rinsing Adsorption of surfactants is not completely reversible because anionics irreversibly chemisorb onto wool and sil/" as observed by both Aic/in ,&&1- and 2olt and Jnorato ,&&@-. Al/yl sulphate and al/yl sulphonate ions react through ion exchange with positively-charged amino and imino end groups of proteins. The actual number of sites available for sorption is p2 dependent" increasing with decreasing p2. Aic/in ,&&3- found that up to 0.3= owf weight of fabric$ of sodium al/yl sulphate was retained by wool fibres under neutral p2 conditions. 2e li/ened the al/yl sulphate ion to a colourless dye. 9auersberger ,&&4- states that surfactants chemisorb less onto sil/ than onto wool and chemisorption of al/yl sulphates onto cotton is proportional to its protein content" most of which is located within the lumen. Dreeland ,&&5- warns that with longer washing time and higher concentrations" surfactants penetrate into the cells of wool cortex and into the lumen and the amorphous regions of cotton fibres. If they go deep they remain after rinsing. 2olt et al. ,&&7" &&'conclude that under normal wool dyeing conditions" anionic surfactants show good substantivity to wool. The factors that influence this are li'uor ratio" length of surfactant side-chain and p2. 8pei and 2ol#em ,&0(- made a connection between the molecular length of anionics and their deposition in /eratin fibre. Weatherburn and %ayle ,&0&- give an overview of the subBect. 8urfactant affinity for the textile surface increases as the si#e of the hydrophobic part increases and the length of the hydrophilic head group/part decreases. The presence of a ben#ene ring increases the strength of the hydrophobic bonding" ma/ing rinsing more difficult. .lectrolytes reduce the electric double layer at the li!uid/solid interface" thereby increasing the adsorption of anionic surfactants. *hee and %allard ,&00-@- investigated the adsorbance of the anionic Jrvus WA and reported that wool adsorbed nine times the level adsorbed by cotton. <olorimetric test methods showed that sil/ adsorbed Jrvus WA 0.51U(.1= owf. )epending on the length of the rinsing time and level of temperature" desorption can be encouraged. ;eft unrinsed" the hydrophobic character of sil/ significantly increased while" after thorough rinsing" its hydrophobic character was normal. The aim of rinsing is to remove the +surfactant-soil micelles+ and the remaining surfactant molecules and soil-carriers. If left in the textile" surfactants and soil carriers" such as 8<9<" attract and aid the diffusion of environmental soils as well as other deteriorating pollutants. *insing problems have been discussed by 2ofen/ de ?raaff ,&03-. To optimi#e rinsing" it should be carried out at the solubility temperature of the surfactant" the soil-carrier and other constituents of the washing solution. When considering only optimum rinsing efficiency" the recommended temperature for rinsing anionic surfactants" at above @( A<" is rather high for historical textiles

unless se!uestering agents arc added to allow the use of lower temperatures$C with non-ionics a lower temperature 03-1( A<$ is effective. 8oil-carriers may be added to the first rinse solution if the textile is heavily soiled. At lower temperatures shorter rinsing times to avoid saturation$ and regular changes of rinse baths are re!uired. The duration of rinsing" as with the duration of washing" depends on many factors" notably the thic/ness and structure of the textile" the possibility of agitation and whether rinsing is carried out in running water or in still baths. The use of hard water for rinsing may result in calcium and magnesium ions replacing soil in the +surfactant-soil micelle+ and soil redeposition may occur. 2ence" the use of soft or deioni#ed water at least in the first two rinse baths is recommended to help to prevent soil redeposition. <omparing the rinsing properties of anionic surfactants and non-ionics shows that anionics can be rinsed out more easily-due to the repelling forces between the textile and washing agent. 2owever" the concentration of anionics in the washed textile may be rather high. Gon-ionic surfactants" having long polar parts" may be bonded to the textile with considerable strength and may be impossible to remove completely. )espite this" their concentration is particularly low" so any residue in the textile will be at a very low concentration. Mse of vacuum suction in wet cleaning Pacuum suction tables were introduced to textile conservation in the late &'5(s by >er/inson ,&04-. <olumbus ,&05- described the washing methods at the Textile 9useum in Washington )< in &'45 and recommended the use of vacuum suction tables in wet cleaning of historical textiles. ;andi ,&07- refers to vacuum suction tables as essential e!uipment for textile conservation wor/rooms. 8mith ,&0'-" )iebhol# ,&1(-" <hristiensen ,&1&-" 2utchinson ,&10-" Dletcher ,&11-" Ashton ,&1@and 2ac/ett ,&13- recommend this e!uipment for cleaning historical textiles. 2owell ,&14introduces the vacuum suction table of the 2ampton <ourt >alace Textile <onservation 8tudio" purchased in &''@. %arnett ,&15- describes the use of a domestic water-extracting vacuum cleaner in the wet cleaning of carpets and tapestries. 2arper ,&17- provides a thorough characteri#ation of the vacuum suction table of the Textile <onservation <entre" M:" and its use for wet cleaning historical textiles. %oth 9aes ,&1'- and %osworth ,&@(- describe tapestry cleaning by aerosol suction. A vacuum suction table has been used in ?ermany for wet cleaning historical textiles as presented by 2elbig ,&@&-. :eyserling/ and Puori ,&@0- reported the use of a custom-made vacuum wash table for wet cleaning of oversi#ed textiles and announced the availability of the table specifications from the <anadian <onservation Institute ,&@1-. .fficiency of washing Dor research purposes" washing effectiveness has been tested using textiles soiled with standard-soil mixture" for example by .astaugh and 8tevens ,&@@-" %oring and .wer ,45" &@3-" .wer and *udolf ,&@4-" *eponen ,&@5-" ;ewis ,7&- and ?inn et al. ,&@7-. A number of approaches has been utili#ed to characteri#e the detergent process" including correlating detergency and electro/inetic phenomena by *ut/ows/i ,&@'-. <ramer ,&3(- provides a range of methods for evaluating soil removal. The degree of cleanness of a textile can be determined by optical assessments and measuring actual soil content. Jptical assessments relate to subBective visual investigation" reflectometry and the photometric and colorimetric attributes" such as whiteness" greyness" yellowness. Actual soil content is usually measured in simulation tests and include microscopic/8canning .lectron 9icroscopic 8.9$ examination" gravimetry" solvent extraction" radiotracer methods in clay and in organic constituents" including artificial sebum. 8oils such as iron oxide can be determined by chemical analysis. .astaugh ,&3&- tried to ma/e a connection between percentage soil removal and detergent formulations. *adioisotope techni!ues are recommended by #hebs ,&30-" while 9orris and >rato ,&('- used V-ray fluorescence analysis as a !uantitative measure for determining paniculate soil

removal from fabrics" as well as colour measurements. 9ee/ ,&31- studied the action of soap and al/ali alone in removing fatty dirt from fibres with a vertical microscope fitted with a reflex viewer and camera. ?entle and 9uller ,7(- controlled the effectiveness by using a video microscope xlJJ. When carrying out experimental washing of archaeological textiles Wolf ,&3@- used visual examination and low magnification photography" as well as 8.9" the latter also used by Jbendorf ,&33" &34-" and >radhan ,&35-. <oo/e et al. ,&37- carried out a research program studying the efficiency of four different cleaning systems for degraded linen" using ob-ective colour measurement to assess soil removal and colour change" tensile testing to estimate changes in strength" image analysis to measure changes in fibre and yarn diameter and yarn spacing" weight loss and 8.9 to assess soil removal and fibre damage. Wal/er ,@1- reports on the first studies of spectrophotometric techni!ues that measured the differences in light remission between soiled and cleaned textiles. <olour measurement with a spectrophotometer before and after washing and calculation of changes in colour delta . values$" whiteness" lightness/dar/ness or yellowness" including the comparison of the colour of a textile to the ?rey 8cale" serve to draw conclusions about cleaning effectiveness. These techni!ues have been applied widely to monitor washing effectiveness" for example by %oring and .wer ,&@7-" *eponen ,&@4- and *hee and %allard ,&01-. 2owever" :issa ,&3'- found that the delta . of remission often does not correlate with the degree of soil removal. The washing effect is normally expressed by comparing the +whiteness+ of a textile before and after treatment. The degree of +whiteness+ of a fabric can be determined by measuring the ultraviolet/visible reflectance spectrum of the textile. (he percentage of light reflected from a textile can be compared to a standard of magnesium oxide ,@7-. The reflectance values of treated and untreated samples can be compared in the same way. 8hashoua ,40" &4(- measured both the percentage reflectance of light at 3(( nm and at the wavelength of maximum reflectance colour of the fabric$ before and after cleaning. The washing power was mathematically calculated and it was found that the higher the reflectance" the more effective the washing. .ffect of washing on fibres and textiles Tensile strength testing has been used to measure the residual strength of textiles. Wolf and 2ughes ,&3@- did not find significant differences between washed and unwashed yarns. %urgess ,&4&compared the long-term stability of naturally aged cotton textile fibres washed in distilled-deioni#ed water" tap water and solutions of calcium bicarbonate 0( ppm$ and calcium sulphate 0( ppm$" using gel permeation chromatography and viscosimetry. Jn the basis of the result of measuring the degree of polymeri#ation )>$ of cellulosic fibres before and after treatment and accelerated ageing she-found that fibres washed with distilled-deioni#ed water or calcium bicarbonate solution showed greatly increased deterioration relative to the control. 2utchins ,&40- investigated the effect of wet cleaning on cotton by measuring weight change" stating that part of the decrease in weight after washing comes from the dissolved deterioration products" while" with the aid of 8.9" >radhan observed dirt particles disappearing from the surface of the fibres after washing ,&41-. Wallenborg examined changes in dimensions" weight" colour" p2" fibre and chemical deposits on the surface on seventeenth century cotton ,&4@-. ?oli/ov and Mstinov ,&43- carried out microscopic investigations on fibres to establish an appropriate cleaning solution. Asnes ,&44- illustrates damage to cotton fibres after wet cleaning treatments using 8.9 micrographs. 2ansen and )erelian describe the effects of wet cleaning on sil/ tapestries. %ased on measuring tensile properties" they found +...sil/ threads of tapestries which became significantly stronger following the washing procedure" but it is extremely unli/ely for this to be a random occurrence+ ,&45" p. 256. Their study did not address the effect of water on long-term strength or the negative effects of swelling of fibres.

Washfastness and colour change of dyes 9asschelein-:leiner ,&47- investigated the solubility of colourants in washing solutions. According to )uff et al. ,&4'-" the washfastness of dyes is determined by several factors" such as the strength of the bonds between the dye and the fibre" the si#e" shape" and levelling characteristics of the dye" the p2 and the actual composition of the washing solution" the temperature and duration of the treatment and the mechanical treatment during washing. In the American 8tandard ,&5(- five classes can be used for characteri#ing washfastness: & very poor" 0 poor" 1 fair" @ good" 3 excellent. TEimFr-%alF#sy and .astop ,&5- give a short overview on the washfastness of direct" acid" basic" mordant and vat dyes. Went# ,51- dyed wool with natural colorants al/anet" annato" bra#ilwood" cochineal" cutch" henna" indigo" lac dye" logwood" madder" weld$ to investigate their colour change and washfastness during wet cleaning. The colour change ratings were obtained by visually comparing the dyed samples after treatment with the American Association of Textile <hemists and <olonsts AAT<<$ ?rey 8cale for colour change. The staining rates i.e. degree of bleeding$ were made on the white fabrics by using the AAT<< ?rey 8cale for staining. The findings led to the conclusion that the anionic sodium al/yl sulphate surfactant Jrvus WA and the non-ionic ethoxylated nonylphenol surfactant" Tergitol G>V" do not cause significant colour changes or staining with the natural colourants tested. )aniels ,&5&- gives a detailed explanation of the reasons for colour change of a number of natural dyes in various p2 conditions. Pago ,&50- reports on the serious colour change of a cochineal dyed wool garment during the cleaning of its silver braiding with sodium hydrogen carbonate solution. The red colour turned to violet due to the change of p2 into the al/aline region ,&5" pp. &@1-4-. )ir/s ,&51- describes the thorough washfastness testing of an American !uilt and the use of the results in the decision-ma/ing concerning its treatment. %ruselius-8charff ,&5@- not only provides a detailed evaluation on the washfastness of synthetic dyes occurring on historical textiles but also ma/es suggestions for the treatment of bleeding dyes. Jger ,&53- investigated the washfastness of modern direct dyes on support fabrics and yarns used for conservation and found that they bleed considerably in washingC the use of these colourants appears to be incompatible with the practical re!uirements of restoration and conservation. %iodegradation of surfactants The ease with which surfactants degrade plays an important role in their selection as concern about their long-term environmental effects increases. An overview on the connection between surfactants and environment has been published by Thomas ,&54- in &'''. Towards the end of the twentieth century serious doubts about the biodegradability of al/yl phenol ethylene oxide non-ionic surfactants have been expressed" noted" for example" by )avidson and 9ilwids/y ,@'" pp. 1)5!7]% It appears that fatty alcohol ethoxylates are biodegradable but this reduces somewhat with increasing amounts of ethylene oxide. 8chic/ ,&55- opposes the use of al/yl phenol ethoxylates because of health conse!uences" slow biodegradation and relative difficulty of rinsing out. In an unpublished typescript >otter ,&57- highlighted the possibility of banning 8ynperonic G in the M: as early as &''0 and ?entle and 9uller ,7(- report that the use of 8ynperonic G was first banned in 8weden due to its partial biodegradability. Gonylphenols have been identified as oestrogenic compounds" which have been lin/ed to both male infertility and breast cancer. )aniels ,&5'- also called conservators attention to the necessity of replacing 8ynperonic G and G)%. A ris/ assessment of using nonylphenol ethoxylates is provided by Wee/s et al. ,&7(- and the problems relating to the sorption of nonylphenol ethoxylates are discussed by 2ayward and Allen ,&7&-. 8wisher ,&70- provides an overview of the connection between the chemical structure and surfactant biodegradation: one conclusion was that the linearity of the hydrophobic group is an important factor. ;inear surfactants are highly biodegradable" highly branched ones are not. The effect of a single methyl branch in an otherwise linear molecule is barely noticeableC however" increased resistance to biodegradability with increased branching is generally observed" particularly

by terminal !uaternary branching. The nature of the hydrophilic group has only a minor influence on the biodegradibility. The clearest examples of such influence are seen in ;>A8" which undergoes biodegradation significantly faster than other amonics and the polyethoxylate non-ionics" where biodegradation is promoted by shorter .J chain length. Increased distance between the sulphonate group and the far end of the hydrophobic group increases the speed of biodegradation. This is /nown as the distance principle. According to 8wisher ,&70-" the problem with al/ylphenol ethoxylates such as 8ynperonic G$ is that the phenol is towards the centre of the molecule. A>.s readily undergo biodegradation when the phenol is lin/ed to the hydrophobic chain at" or near" the end. .thoxylates of linear fatty acids and fatty amides are easily degraded even with ethoxylation as high as .JH0(. The use of a sugar as the hydrophilic group does not result in any spectacular improvement in biodegradability" but falls in line with the usual principles. 8elected case histories using surfactants and other wash bath additives Gaithani and :harbade ,&71- give a valuable overview on the a!ueous cleaning methods of historical textiles. ?entle and 9uller ,7(- followed a repeated se!uence of washing and rinsing when carrying out washing of historical textiles for research purposes. <ase histories on wet cleaning of archaeological textiles have been published by Dlury-;emberg ,15-" 2illyer ,&7@- and Gagy ,&73-. 9ethods of wet cleaning of historical textiles are described by *ice ,&74-" Dinch and >utnam ,&75" &77-" 9asschelein-:leiner ,&7'-" ;andi ,&0'- and >ertegato ,&'(" &'&&. ;andi ,&'0may have been the first to introduce a modern washing table to textile conservation laboratories in a paper published &'44. *esults of thorough research into wet cleaning of historical textiles is provided by ?unilla ,&'1" &'@-. 8chneider ,&'3- reports on removing &&@g soiling and possibly" in the present author+s opinion" deterioration products of fibres$ from a sacred coat by wet cleaning. The +routine+ wet cleaning methods of the %altimore 2ouse Textile <onservation Wor/shop were discussed by Wolf et al. ,&'4-. %ehar ,&'5, gives an overview and flood and bath washing is described by 2oward ,&'7- for wet cleaning carpets. The use of foam from 2ostapon T is common in the Abegg-8tiftung" 8wit5.erland" and in many other wor/shops. >ata/i ,&''- reports using the foam of a (.3 g/litre 2ostapon T anionic surfactant solution for cleaning a historical textile. Washing of large textiles is a particularly difficult tas/" as reported by Di/ioris ,0((-" )avies ,'5-" the Textile 8tudio" 2ampton Court [*+1], ,eyserli -k [*+*], .alda e ,0(1- and 9ar/o et al. ,0(@-. Colli s ,0(3-" for example claims that the soa/ing of the head!uarters tent of ?eorge Washington too/ 43 hours to loosen mud stains and other soil. <onclusions It is natural that a literature review also provides a historical overview. >ublications on textile conservation from the &'3(s and &'5(s show the strong influence of industry on the surfactants and other ingredients used in wash baths for historical textiles. Wor/ing with conservators" scientists entering conservation from an industrial bac/ground" sooner or later recogni#ed the limits in the use of the enormous number of different washing agents available and applicable to industry. *esearch in the &'7(s and &''(s resulted in wash bath recipes much more closely tailored to conservation. 2owever" there are several +grey areas+" such as the connection between critical micelle concentration" cloud point and :rafft pointC how to determine the remained adsorbed surfactant in the washed historical textile in 8eptember 0((( 2owell and <arr ,0(4- presented a promising new method using V-ray >hotoelectron 8pectroscopy$C or simply" what is the appropriate washing time. After finding appropriate surfactant and washing solution compositions" many wor/shops started to use predominantly one type of surfactant routinely see the popularity of Jrvus WA in the M8A and 8ynperonic G in the M:$" despite there-being many varied surfactants available and recommended in the conservation literature. The method of choosing particular surfactants and washing solutions according to the specific need of the obBect to be treated" or using them in combination is still rare.

Dast dissemination of information is characteristic of recent years but not of the past: although *ice published on the use of amomc detergent in the first" and non-ionic in the second wash bath in &'44 ,'3-" it was only in &''3 that ?entle and 9uller systematically researched the use of mixtures of amonics and non-ionics in the same wash bath [)+]% )ating from &''3" Wal/er+s recommendation to start with a lower" and end with a higher 2;% surfactant in a two-step washing process seems to have had little influence on the textile conservation field [4/]% The environmental concerns" both relating to conservators+ health and the biodegradability of surfactants" necessitated new researches in this field" not for the purposes of the conservation of historical textiles" but for the conservation of human beings and their environment. It is true that there are negative remar/s on the health effects and slow biodegradability of some popular surfactants in specialist literature before 8chic/+s wor/ of &'44 ,&55-C however" the first warning relating to the use of nonlyphenol ethoxylates in the field of textile conservation came from >otter in &''0 ,&57-" followed by ?entle and 9Wller+s &''3 thesis ,7(- and ending with )aniels+ dramatic announcement in &''' ,&5'-. Gow" as increasing numbers of conservators and scientists are searching for a replacement for 8ynperonic G" it should be as/ed why it too/ such a long time to start dealing seriously with the problem. Also" it may be !uestioned" as did 2owell ,0(4-" whether the very small !uantities" which are used highly diluted in textile conservation" are really the cause of such a serious problem or if this is much more a problem for industry. In conclusion" the author hopes that the above review shows the importance of studying the +industrial+ literature" of allowing enough time for a thorough conservation-related +critical+ adaptation and of being sufficiently fast in following initiatives towards new research. *eferences & )unan-*ees" X." +The cleaning of historic textiles -methodological and scientific aspects+ i >ertegato" D." ed." 7onservation and 8estoration of Textiles 9roceedings of the :nternational 7onference, 7oino ;2<=, <I88T-I.ombardy 8ection" &'70" pp. &'&-4. 0 .astop" ). and %roo/s" 9." +To clean or not to cleanY+ in %ridgland" 6." ed." 9reprints of the ; lth Triennial >eeting of the :7?> 7ommittee for 7onservation, din!urgh, 6ames K 6ames" ;ondon" &''4" pp. 475-'&. 1 D.astop" ). and %roo/s" 9." +)ifficult decisions in cleaning: the evide tal value of soils and creases+ in 0. hemaligentreffen der @hegg-5tiftitng, 8eferate der Tagung, Aovem!er ;22B, Abegg8tiftung" &''4" pp. &(-&'. @ 2all" *. and %arnett" 6." +A fifth dynasty funerary dress in the >etne 9useum of .gyptian Archaeology: its discovery and conservation+" Textile "istory &4" no. &" &'73" p. &0. 3 )odds" W.Z +<onsolidation of mud on a World War I uniform+" @ustralian :nstitute for the 7onservation of 7ultural >aterial (AICCM) Aewsletter 03" &'77" p. 5. 4 %roo/s" 9." <lar/" <" .astop" 0% and 1ets"hek, <" +*estoration and conservation issues for conservators+" in Jddy" A." ed." 8estoration/ :s it @ccepta!leC, %ritish 9useum Jccasional paper ''" )epartment of <onservation" ;ondon" &''@" pp. &(1-00. 5 %roo/s" 9." ;ister" A." .astop" ). and %ennett" T" +Artefact or informationY Articulating the conflicts in conserving archaeological textiles+ i *oy" A. and 8mith" >." eds." @rchaeological 7onservation and its 7onse)uences, 9reprints of the 7ontri!utions to the IIC 7ongress, 7openhagen, II<" ;ondon" &''4" pp. &4-0&. 7 2oha se , :." +>erfumed garments" their preservation and presentation +...the good smell of old clothesN in %ridgland" 6." ed." 9ostprints of the ;Dth Triennial >eeting of the :7?> Committee for 7onservation, #yon, 6ames K 6ames" ;ondon" &'''" pp. 415-@0. ' 8tauffer" A." +8ome comments on the cleaning of archaeological textiles+ in Timar-%ala#sy" [C. and .astop" )." eds." :nternational 9erspectives on Textile 7onservation, Archetype" ;ondon" &''7" pp. &3'-4&.

&( Windsor" )." +To clean or not to clean+ in .wer" >. and 9c;aughlin" %." eds." 9ostprints of the @l7-Textile 5peciality .roup >eeting, AI<" &''3" pp. 1'-3(. & & Timar-%ala#sy" A." 9atefy" ?y. and <sanyi" 8." +.ffect of stains and stain removal methods on historical textiles+ in %ridgland" 6." ed." 9reprints of the ;=th Triennial >eeting of the :7?> 7ommittee for 7onservation, %ashington -7, 6ames K 6ames" ;ondon" &''1" pp. 11(-3. &0 A/ar" A." The 5oiling of Textile >aterials, 9.>hil" thesis." Mniversity of ;eeds" &'50" pp. 4@, unpublished typescript. &1 9c:innon" A.6. and 9c;aughlin" 6.*." +The dependence of carpet soiling on fibre properties" soil composition" and carpet construction+ in :nternational %ool Textile 8esearch 7onference 9roceedings no 1" &'73" pp. 114-@3. &@ >atterson" 2.T. and ?rindstaff" T.2." +8oil release by textile sutfactants+ in 8chiec/" 9.6." ed." 5urface characteristics of fi!ers and textiles, Diber 8cience 8eries 5" 9arcel )e//er" &''3-&''5" <hapter &0" pp. @@7-'@. &3 >ovve" W.<." +;aundry soils+ in <utler" W.?. and )avis" *.<." -etergency, Theory and Test >ethods, 9art ;, 8urfactant 8cience 8eries 3" 9arcel )e//er" &'50" p. 17. &4 Weber" *." ;ohr" A. and %oggering" 2." +Waschen und >flegen von Textilien aus <hemifasern+" >elliand Textil!enchtc &" &'7&" pp. '@-&(&. &5 Timar-%ala#sy" B. and .astop" )." 7hemical 9rinciples of Textile 7onservation, %utterworth2einemann" ;ondon" &''7. &7 Armstrong" 6.?." )owd" ).?." >i/e" 9.P. and #titt, #%, 34 furnace puff-bac/: the uni!ue problem of soot on ob5e"ts and costumes+ in 9reprints of 9apers 9resented at the Ainth @nnual >eeting, 9hiladelphia, AI<" &'V&" pp. &(-&'. &' <arter" 6.W." +Iron stains on textiles: a study to determine their nature and to evaluate current treatments+ m de Droment" )." ed." 9reprints of the Eth Triennial >eeting of the /<J9 7ommittee for 7onservation, 7openhagen, I<J9 with the 6. >aul ?etty Trust" &'7@" pp. 7@.' &&&@. 0( Zordan" .." +.ntfernung von :al/verput# aus einer mittelalterichen Wollstic/creis und ihre *estaurierungsproblemati/+" @r!eits!latter fiir 8estauratoren 0&" no. 0" &'77" pp. &(4-&(. 0& 2utchms" 6." The solu!le components of degraded cellulose, 9.8c. thesis" Gorth <arolina 8tate Mniversity" 8chool of Textiles" &'7&" unpublished typescript. 00 2ersh" 8.>." 2utchins" 6." :err" G. and Tuc/er" >.A." +The soluble components of degraded cellulose+ in >ertegato" D." ed." 7onservation and 8estoration of Textiles. 9roceedings of the :nternational 7onference, 7omo ;2<=, <I88T-;ombardy 8ection" &'70" pp. 75-'3. DF Andrasi/" I." +Jxidi#ed oil stains+" :G: Bulletin/ Technical, International Dabncare Institute" &'74" p. 0. 0@ 9oreland" %." +Jxidi#ed oil stains+" :G: Ga!ncare Aews &4" no. &0" )ecember &'75" p. &@. 03 <aneva" ?." Gugari" 9.>. and 8alvadori" J." Biology in the 7onservation of %or(s of @rt, I<<*J9" &''&" pp. 4(-&. 04 %allard. 9.W." +The removal of crosslin/ed synthetic latex from carpets: preliminary results+ in %ridgland" 6." ed." :'ostpnnts of the ;=th Triennial >eeting of the :7?> 7ommittee for 7onservation, %ashington -7, 6ames K 6ames" ;ondon" &''1" pp. 11&-7. 05 *ice" 6.W." NThe characteristics of soils and stains encountered on historic textiles" >rinciples of Textile <onservation 8cience no. P Textile >useum Hournal, )ecember &'4@" pp. 7-&5. 07 9atteini" 9." Tosini" I." ?iorgi" 9. and >alei" ?." + .valuation of possible methods of cleaning the ?pus @nglicanum cope of >ope >ius II+ in %ridgland" 6." ed." 9reprints of the ;Dth Triennial >eeting of the :7?> 7ommittee for 7onservation, #yon, 6ames K 6ames" ;ondon" &'''" pp. 403-1(. 0' 9oncrieff" A. and Weaver" ?." 7leaning, 8cience for <onservators" %oo/ 0" <rafts <ouncil" ;ondon" &'71. 1( 2ofen/ de ?raaff" 6." +)etergents and their function in washing old textiles+ in :7?> 7ommittee for >useum #a!oratories, %russels" &'45" 00 pp.

1& :issa" .." +:inetics and mechanisms of detergency >art III: .ffect of soiling conditions on particulate soil detergency+" Textile 8esearch Hournal @'" no. 5" 6uly &'5'" pp. 17@-'. 10 8aito" 9." Jtani" 9 and \abe" A" +Wor/ of adhesion of oily dirt and correlation with washabihty+" Textile 8esearch Hournal 33" no. 1" 9arch &'73" pp. &35-4@. 11 8mith" 8. and 8herman" >.J." +Textile characteristics affecting the release of soil during laundering >art I: A review and theoretical consideration of the effect of fiber surface energy and fabric construction on soil release+" Textile 8esearch Hournal 1'" no. 3" 9ay &'4'" pp. @@&]@. 1@ *ice" 6.W." +The wonders of water in wet cleaning" >rinciples of textile conservation science PI+ Textile >useum Hournal D, no.l" )ecember &'44" pp. &3-00. 13 <oo/e" %. +<reasing in ancient textiles+" 7onservation Aews F4, &'77" pp. 05-1'. 14 Dlury-;emberg" 9." +The care of historic fabrics illustrated by the grave garments of 8igismondo >andolfo 9alatesta+ in >ertegato" ." ed." 7onservation and 8estoration of Textiles. 9roceedings of the :nternational 7onference, 7omo ;2<=, <I88T-;ombardy 8ection" &'70" pp. 0(0-5. 15 Dlury-;emberg" 9." Textile 7onservation, Abegg-8tiftung" &'77. 17 *ice" 6.W. +)ry cleaning versus wet cleaning for treating textile artifacts+" Bulletin of the @merican .roup-:l7 &0" no. 0" April &'50" pp. 3(-3. 1' Torracca" ?." 5olu!ility and 5olvents for 7onservation 9ro!lems, I<<*J9" @th+edn" &''(" p. 35. @( 8eth-8mith" A. and Wedge" T." +Animal glue removal from &4th century Dlemish tapestry fragments: a comparative study of three cleaning methods+" 7onservation Aews 3'" 9arch &''4" pp. 43-5. @& The ?uild of <leaners and ;aunderers" @n :ntroduction to #aundry 7hemistry, The ?uild of <leaners and ;aunderers" 89/@'3@/&" &'74" pp. @-3. @0 2ofen/ de ?raaff" 6." +The constitution of detergents in connection with the cleaning of ancient textiles+" 5tudies in 7onservation &1" &'47" pp. &00-@&. @1 Wal/er" )..." +8urfactants in textile conservation+ in .wer" >. and 9c;aughhn" %." eds." 9ostpnnts of the 7onference of the @l7-Textile 5peciality .roup, AI<" &''3" pp. 0'-1@. @@ Arai" 2." +8tudy of detergency I. .ffect of the concentration and the /ind of detergent in hard water+" Hournal of the @merican ?il 7hemists' 5ociety @1" 9ay &'44" pp. 1&0-&@. @3 %ede" )." +Water - what about itY+ in .wer" >. and 9c;aughlin" %." eds." 9ostpnnts of the 7onference of the @:7-Textile 5peciality 7roup, AI<" &''3" pp. '-&&. @4 2eald" 8." +)eiom#ed water and its reactivity R could it be damagingY+ in .wer" >. and 9c;aughlin" %." eds." 9ostprtnts of the 7onference of the @:7-Textile 5peciality .roup, AI<" &''3" pp. &0-&@. @5 >henix" A. and %urnstoc/" A. +The removal of surface dirt on paintings with chelating agents+" The 7onservator &4" &''0" pp. 07-17. @7 2ofen/ de ?raaff" 3., +8ome recent developments in the cleaning of ancient textiles+ in %romelle" G.8. and Thomson" ?." eds." 5cience and Technology in the 5ervice of 7onservation, II<" ;ondon &'70" pp.'1-'3 @' )avidson" A. and 9ilwids/y" %." 5ynthetic -etergents, ?eorge ?odwin ;td" ;ondon and 6ohn Wiley K 8ons" Gew \or/" 4tn edn" &'57. 3( Geiditch" J.W." +)efinition of terms <hapter + in <utler" W.?. and )avis" *.<." -etergency. Theory and Test >ethods, 9art ;, 8urfactant 8cience 8eries 3" 9arcel )e//er Inc." &'50" p. '. 3& 9oore" 9.A." -etergents, A Mnilever .ducational %oo/let" *evised Jrdinary 8eries no. &" Mnilever ;imited" &'45" pp. 1-@. 30 Given" -un." W.W." Gundamentals of -etergency, *emhold >ublishing <orporation" &'3(" pp. @3-7. 31 )urham" :." 5urface @ctivity and -etergency, 9acmillan K <o. ;td" ;ondon" &'4&" pp. 04-5. 3@ 6a/obi" ?. and ;ohr" A." -etergents and Textile %ashing, 9rinciples and 9ractice, P<2 Perlagsgesellschaft" Weinheim" &'75.

33 ;infield" W." ed." @nionic 5urfactants, 8urfactant 8cience 8eries 5" 9arcel )e//er Inc." &'54. 34 8chic/" 9.6." ed." Aoniomc 5urfactants, 8urfactant 8cience 8eries &" 9arcel )e//er" &'44 35 2ofen/ de ?raaff" 6." +8ome thoughts about cleaning ancient textiles+ in 5ymposium 7onservation of Glags, 8iI(smuseum, @msterdam, ;2EE, IA9A9-Textielcommissie 9usea" &'7(" pp. &('-&& 37 8mith" ).;." 9atheson" :.;. and <ox" 9.D." +Interactions between linear al/ylben#ene sulfonates and water hardness ions III 8olubili#ation and performance characteristics of <a ;A8$5+" Hournal of the @merican ?il 7hemists' 5ociety 40" no. '" 8eptember &'73" pp. &1'']&(0. 3' Ta/ami" 9." Gunon as a cleaning agent for historic textiles/ a preliminary investigation of its surfactant properties and cleaning effect, )iploma Thesis" The Textile <onservation <entre" Mniversity of 8outhampton" Winchester" 0(((" unpublished typescript. 4( .mbree" 6.;." +Wash day woes of the textile conservator: laundry methods of the turn of the century+" @rs Textrina, Hournal of Textiles and 7ostume VVIII" August &''3" pp. 51'3. 4& <amC." <" NTraditional techni!ues used for cleaning" restoring and caring for textiles i the &'th and 0(th centuries+" Bulletin of the :nstitute for the 7onservation of 7ultural >aterial, @ustralia '" nos. & and 0" &'71" pp. @1-45. 40 8hashoua" \." +Investigation into the effects of cleaning natural" woven textiles by a!ueous immersion+ i ?rimstad" :." ed." 9reprints of the 2th Triennial >eeting of the :7?> 7ommittee for 7onservation, -resden, I<J9" &''(" pp. /1/!1)% 41 <#erwins/e" >." -er Einsatz von Saponin zuf Reinigung histonscher 5eidenstoffe, )iploma Thesis" Dachhereich *estaurierung und :onservierung von ,u st! und :ulturgut der Dachhochschule :oln" &''5" unpublished typescript. 4@ lsu-ii" :." 5urface @ctivity. 9rinciples, 9henomena, and @pplications, Academic >ress" &''7" p. @ I. 43 )illan" :.W." +.ffects of the ethylene oxide distribution on nonionic surfactant properties+" Hournal of the @merican ?il 7hemists' 5ociety 40" no. 5" 2uly &'73" pp. & &@@-3&. 44 >orter" $%6%, Handbook of 5urfactants, %lac/ie Academic K >rofessional" &''&" reprinted" &''1" pp. @0-@3. 45 %oring" 9. and .wer" >." +8urfactant comparison test+ in :rueger" 6." ed." 9roceedings of the 9aintings and Textiles 5pecialty 7roups Hoint 5ession, A&<" &''&" pp. @&-4&. 47 0el"roi7, ?. and %ureau" <" +A new detergent formulation+ The Textile >useum Hournal 0' and 1(" &''(-&''&" The Textile 9useum" &''&" pp. 3'-4@. 4' %igler" G." Aetzen und Waschen, <iba-?eigy *undschau" )ie Tenside" &'5&-0" pp. 0@-10. 5( Ward" T.;. and %enerito" *.*." +Testing based on wettability to differentiate washed and unwashed cotton fibers+" Textile 8esearch Hournal 33" no. &" 6anuary &'73" pp. @&-3. 5& ;ange" I;" +>hysical chemistry of cleansing action& in 8hinoda" :." ed." 5olvent properties of surfactant solutions, 8urfactant 8cience 8eries 0" 9arcel )e//er" &'45" pp. & &5-77. 50 2utchinson" .. and 8hinoda" :." +8olvent properties of surfactant solutions+ in 8hinoda" :." ed." 5olvent properties of surfactant solutions, 8urfactant 8cience 8eries 0" 9arcel )e//er" &'45" pp. &1-&4. 51 Went#" 9." +.xperimental studies on the effect of a!ueous and o a'ueous treatments on historic textiles+ i Geedles" 2.8. and Qeronian" 8.2." eds." "istoric Textile and 9aper >aterials/ 7onservation and 7haracterisation, Advances i <hemistry 8eries 0&0" American <hemical 8ociety" &'74" pp. *118/+% 5@ #ka-erli d, >. +Textile cleaning with tensides and/or en#ymes+" 8engoring vid textil(onservering idag och i framtiden *Textile 7leaning and 7onservation Today and Tomorrow,, 8eminar" Army 9useum" 8toc/holm" Arme 9useum *apportsene 4" &''1" pp. &5-0&. 53 Taylor" *.6." Theory of -etergency, A Mnilever .ducational %oo/let" Advanced 8eries" no. 5" Information )ivision" Mnilever ;imited" &'4'" &4 p.

54 [uhasz, .. and ;el/esne .ros" 9." eliileta(tiv @nyago( Jseh(onyve %oo/ of surface active agents$" 9us#a/i :onyv/iado" &'5'" pp. &04-17. 55 Qi/a" .l." +Msing non-ionic surfactants+ Hournal of the @merican ?il 7hemists' 5ociety &" no. &3" &'4'" pp. 04/101-1&/107. 57 *ice" 6.W." +<haracteristics of detergents for cleaning historic textiles. >rinciples of textile conservation science" Go. 9&&3, Textile >useum Hournal II" no.l" &'5(" pp. 01-5. 5' :issa" .." +:inetics of soil release+" Textile 8esearch Hournal @&" 8eptember &'5&" pp. 54(-5. 7( ?entle" G. and 9uller" 8." +An initial studv of detergents and washing recipes for use in the conservation of textile obBects+" 7onservation Aeivs 37" Govember &''3" pp. 33-'. 7& ;ewis" 6." 5ummary of an investigation into mixtures ofanionic and nonionic surfactants for wet cleaning historic textiles, )iploma Thesis" The Textile <onservation <entre" <ourtauld Institute of Art" ;ondon" &''4" unpublished typescript. 70 Brochure BKF; -, <iba ?eigy" & p. and -escription of $ieralon !", %A8." 1pp. 71 8tupel" .;" S#nthetische %ash- and 8einigungsmittel, :oradin Peiiag" &'35. 7@ 6ones" T.?." +)irt removal+" chapter @ in Cutler, W. and :issa" .." eds." 5urface @ctivity and -etergency, 9acmillan K <o. ;td" ;ondon" &'4&" pp. 50-&&7. 73 2arris" ,. <" +)etergency+" m 8chic/" 9.6. ed. Aonionic surfactants, 8urfactant 8cience 8eries &" 9arcel )e//er" &'45" p. 5(4. 74 8chonfeldt" G." 5urface @ctive thylene ?xide @dducts, >ergamon" Jxford" &'4'" pp. 174-@@&. 75 8mith" AAP. and ;amb" 9.2." +The prevention of soil redeposition i the cleaning of ancient textiles+ in 9reprints of the Bth Triennial >eeting of the :7?> 7ommittee for 7onservation, ?ttawa, &'7&" pp. 7&/'/@-&. "" ;chmann" )." +*estaurieren und :onservieren histonscher lextilen " @r!eits!latter fiir 8estauratoren, &/5@" ?ruppe &(" Textiiien" pp. 05-11. 7' Wveth" >." 8esearch 9roposal, Internal *eport" The Textile <onservation <entre" <ourrauld Institute of Art" ;ondon" &''4" unpublished typescript. '( <ollins" 9." "ow to wet clean uudyed cotton and linen, 8mithsonian Institution" 9useum of .istory and Technology textile ;aboratory" Washington )<" Information ;eaflet @57" & '45" & & pp. '& 2ogberg" 8." +<leaning sil/ velvet+" 5!'T-Hu!ilee 7onference, 5il( - -ifferent @spects, 8vens/a Doreningen for Textil/onservering" &''5" 1 pp. '0 )aniels" P. and 8hashoua" \." +Wet cleaning of paper and textiles: similarities and differences+ in %utterfield" . and .aton" ;." eds." 9aper and Textiles. The 7ommon $%ound& 9reprints of the 7onference held at The Burrell 7ollection, .lasgow, 88<*" &''&" pp. &'-0@. '3 <anadian <onservation Institute" %ashing non -coloured textiles, CC& Gotes &1/5" <<T" Jttawa" &st printing &'74" 0nd printing &'77C @nionic -etergents, <<I Gotes &1/'" <<T" Jttawa" &'71. '@ 9ofatt" .." -etergents, <<I *eport A*8 no. &57&" <<I" Jttawa" &'7&. '3 *ice" Z.W." +An heirloom patchwor/ !uilt and its conservation problems+" 5tudies in 7onservation &&" no.l" :ebruary &'44" pp. &-5. '4 Co7, 9.." %orys" G.. and 9atson" T.>." +Interactions between ;A8 and nonionic surfactants+" Hournal of the @merican ?il Chemists' 5ociety 40" no. 5" 6uly &'73" pp. &&1'-@1. '5 )avies" P" +Wet cleaning of the dining room curtains Mppar/ .ouse3 and +Wet cleaning of the small drawing room curtains Mppar/ 2ouse+ in 9ar/o" :." ed." Textiles in Trust, Archetype in association with the Gational Trust" ;ondon" &''5" pp. &3'-41 and &4@-5. '7 .lofen/ de ?raaff" 6." +<leaning ancient textiles+ in >ertegato" ." ed." 7onservation and 8estoration of Textiles. 9roceedings of the :nternational 7onference, 7oma ;2<=, <I88T;ombardy 8ection" &'70" pp. 40-43.

'' ?iuntmi" <. and %ede" ). +The conservation of a group of paracas mantles+ in 8tefanaggi" 9." ed." #a 7onservation des Textiles @ncieus, Hournees d'ftudes de la S(IIC, Ange%s, 8II.<" &''@" pp. &4'-5'. &(( ,a5ita i, G." +A retrospective of &'51 conservation treatment on a 9unghal court robe with the pigment-painted poppy flower pattern+ in >auloci/" <. and Dlaherty" 8." eds." The 7onservation of ;<th century painted sil( dress, The <ostume Institute" The 9etropolitan 9useum of Art and the ?raduate >rogram i <ostume 8tudies" Gew \or/ Mniversity" &''3" pp. &&7-0'. &(& Qongyou" ." +The preservation of textile unearthed from G. & 9ausoleum of :ing Oin in Deng Viang <ounty of 8aanxi >rovince+ in 9roceedings of the 7 7hina wor(shop on preservation of cultural heritages. Lian, 5haanxi, 9.8. of 7hina. 5eptem!er D4-F=, ;22;, (eti, Na;oli, &''0" pp. @01-1(. &(0 :iefer" :." +Interdisciplinary philosophies: Textiles and >aper: a <ommon ?round+ in The @:7 Textile 5pecialty .roup 9ostpnnts, AI<" &''@" pp. 5-&3. &(1 <usseil" 8." +)ifferent methods or different choices+ in Ti+mar-%ala#sy" c. and .astop" )." eds." :nternational 9erspectives on Textile 7onservation, Archetype" ;ondon" &''7" pp. &(7-&(. &(@ ?lover" 6.9." +Textile conservation in Gorth West .ngland+ m >ertegato" D." ed." 7onservation and 8estoration of Textiles. 9roceedings of the :nternational 7onference, Cotno ;2<=, <I88T-;ombardy 8ection" &'70" pp. 0(7-&@. &(3 %urgess" 2." )uffy" 8. and Tse" 8." +Investigation of the effect of al/ali on cellulosic fibres >art &: rag and processed wood pulp paper+ in %utterfield" D. and .aton" I.." eds." 9aper and Textiles. The 7ommon .round. 9reprints of the 7onference held at The Burell 7ollection, .lasgow, 88<*" &''&" pp. *<!47, &(4 2ofen/ de ?raaff" 6." personal communication" &''&. &(5 8henai" P.A." +Jrganic textile chemicals - historical introduction+" Textile -yer M 9rinter, 07 )ecember &'77" pp. &3-&'. &(7 9aison <hevalier" Aubusson" 8apport de 5tage/ '-etermination de la concentration ideale de detergent pour le nettoyage d'un textile histon)ue', <hristophe %ureau .cole Gormale 8uperieure" &'77" 03 pp. &(' 9orris" 9.A. and >rato" 2.2." +The effect of wash temperature on removal of ;a i"ulate and oily soil from fabrics of varying fiber content+" Textile 8esearch Hournal 30" no. 3" April &'70" pp. 07&-4. &&( 2ewitt 9yers" ?." +>rinciples of practical cleaning for old and fragile textiles+" >useum Aews Technical 5upplement B, Debruary &'43" pp. 3(-0. &&& 2owell" ). and Darnsworth" 6." +Jperation Wetclean - a review" Jperation Wetclean R an analysis of results&" 7onservation Aews 50" 6uly 0(((" pp. 31-4. &&0 <artwright" 2. and <olombini" A." +)etergent monitoring during the washing process at the Iextile <onservation 8tudios" 2ampton <ourt >alace+ in %ridgland" 6." ed." 9reprints of the ;=th Triennial meeting of the :7?> 7ommittee for 7onservation, %ashington -7, ;22F, pp. 0'1-7. &&1 Aic/in" *.?." +<ommunication: the adsorption of sodium al/yl sulphates on wool and other textile fibers+" Hournal of the 5ociety of -yers and 7olounsts 4(" no. 1" 9arch &'@@" pp. 4(-3. &&@ 2olt" ;.A. and Jnorato" 6." +8ubstantivity of various anionic surfactants applied to wool+" Textile 8esearch Hournal 3'" no. &&" Govember &'7'" pp. 431-5. &&3 Aic/in" *.?." +The adsorption of sodium al/yl sulphates on wool and other textile fibres+" Hournal of the 5ociety of -yers and 7olounsts 4(" no. &(" Jctober &'@@" pp. 044-75. &&4 9auresberger" 2." ed." Textile Gi!res, Wiley and 8ons" &'@5" p. 04'. &&5 Dreeland" ?.G." ?uise" ?.%. and *ussel" I.9." +8orption and analysis of some nonylphenol ethoxylate surfactants on wool+" Textile 8esearch Hournal 33" no. 4" 6une &'73" pp. 137-40. &&7 2olt" ;.A." :elson" 6.8." and *eddie" *.G." +8ubstantivity of various anionic surfactants applied to wool. >art I and II+" Textile 8esearch Hournal 3'" &'7'" pp. 331-435. &&' 2olt" ;.A." :elson" 6.8." and *eddie" *.G." +8ubstantivity of various anionic surfactants applied to wool. >art I and I>" Textile 8esearch Hournal 40" no. 1" 9arch &''0" pp. &@&-&@1

&0( 8pei" 9. and 2ol#em" *." +9olecular length dependent deposition of sodium al/yl sulphates in /eratin fibre+" >elliand Textilhenchte '" &''(" .10'" 5&" pp. 5(4-5. &0& Weatherburn" A.8. and %ayle" <.2." +The sorption of synthetic surface active compounds by textile fibres+" Textile 8esearch Hournal 00" )ecember &'30" pp. 5'5-7(@. &00 *hee" 2. and %allard" 9." +The chemical interaction of surfactants with fibres" especially with sil/+ in 9ostpnnts of the >eeting of the @l7 Textile 5pecialty .roup, AI<" &''1" pp. 07-15. &01 *hee" 2. and %allard" 9." +*esidues of surfactant on sil/+ in %fidgland" 6." ed." 9reprints of the ;=th Triennial meeting of the :7?> 7ommittee for 7onservation, %ashington -7, ;22F, pp. 105'. &0@ %allard" 9.W. and *hee" 2." NThe effect of surfactant residues on sil/+ in 5vens(a Goremngen for Textil(onservenng Hu!ilee 7onference. 5il( - -ifferent @spects, 8.T" &''5" 4 pp. &03 2ofen/ de ?raaff" personal communication" &''4. &04 >er/inson" *.;." +)esign and construction of a suction table+" Hournal of the @merican :nstitute for 7onservation 0(" nos. & and 0" &'7&" pp. 14-@(. &05 <olumbus" 6.P." +Washing techni!ues at the Textile 9useum+" ::7-@. Bulletin 5" no. 0] &'45" pp. &@-&4. &07 ;andi" 8." The Textile 7onservator's >anual, %utterworth-2einemann" ;ondon" 0nd edn" &''0" pp. 1' K '1-3. &0' 9elville 8mith" ;." +<onservation practices at the 9useum of Dine Arts" %oston+ in >ertegato" D." ed." 7onservation and 8estoration of Textiles 9roceedings of the :nternational 7onference, 7otno ;2<=, <I88T-;ombardy 8ection" &'70" pp. 03&-7. &1( )riebhol#" P." +The use of suction table in textile and paper conservation+" 8eport of the Textile 7onservation .roup 1" no. 1" )ecember &'7(" pp. 0-3. &1& <hristiensen" <" +The suction table for use on paintings and textiles+" @:7 Aews &5" no. 0" &''0" pp. &-@. &10 2utchinson" %." +8uction table used at the Textile <onservation ;ab at the <athedral <hurch of 8t. 6ohn the )ivine+" Textile 7onservation .roup Aewsletter 1" &''0" pp. 1-@. &11 Dletcher" 8." +8uction for locali#ed treatment of paper and textiles. >art I - suction techni!ues used on wor/s of art on paper+" report issued at the 8cottish 8ociety for <onservation and *estoration <onference" 9aper and Textiles/ the 7ommon .round, held at the Burrell 7ollection, .lasgow, 88<*" &''&" 7 pp." unpublished typescript. &1@ Ashton" 9." +8uction for delocali#ed treatment of paper and textiles. >art II - Pariations in behaviour of paper" textiles and e!uipment used i suction dis/ treatments+ in %utterfield" D. and .aton" I.." eds." 9aper and Textiles/ the 7ommon .round. 9reprints of the 7onference, held in the Burrell 7ollection, .lasgow, 88<*" &''&" pp. 3'-4'. & 13 2ac/ett" 6." 9ossi!le designs for a vacuum suction ta!le for the textile conservation la!oratory, *eport" Dine Arts 9useum 8an Drancisco" &''1" && pp" unpublished typescript. &14 2owell" )." +Gew vacuum table design for use with textiles+" 7onservation Aews 3@" &''@" p. &0. &15 %arnett" 6." +The use of a domestic water extracting vacuum cleaner in the wet cleaning of carpets and tapestries+ in Timar-%ala#sy" ). and .astop" )." eds." :titernational 9erspectives on Textile 7onservation, Archetype" ;ondon" &''7" pp. 0'-1&. &17 2arper" 9.T." @n :nvestigation into the use of vacuum suction ta!les for dry and wet cleaning historic textiles, )iploma *eport" >ostgraduate )iploma in Textile <onservation" Textile <onservation <entre and <ourtauld Institute of Art" Mniversity of ;ondon" &''3" unpublished typescript. &1' 9aes" \" +Tapestry cleaning by aerosol suction+ in Timar-%ala#sy" f" and .astop" )." eds." :nternational 9erspectives on Textile 7onservation, Archetype" ;ondon" &''7" pp. 10-1. &@( =os>orth, )." +Wet cleaning a fragile tapestry using the de Wit system+" 7onservation Aews 43" 9arch &''7" pp. @'-3&.

&@& 2elbig" 2." +.insat#moghch/eiten fur einen Giederdruc/tisch in der Textilrestaurierung+" @r!eits!latter fur 8estauratoren 0/'@" ?ruppe &( Textilien" &''@" pp. 0((-&(. &@0 :eyserlmg/" 9. and Puori" 6." +Wet cleaning an oversi#ed textile on a vacuum wash table+ in 9ostpnnts of the @:7 Textile 5pecialty .roup, AI<" &''3" pp. 5'-74. &@1 <anadian <onservation Institute" +acuum %ash Ta!le, Treatment 8eport, appendix ?" pp. &1@-3" available from <<I .xtension 8ervices with the structural drawing" <<I" &(1( Innes *oad" Jttawa" Jntario :&A (93" <anada. &@@ .astaugh" G. and 8tevens" )." Aotes on washing solutions, The Textile <onservation <entre" <ourtauld Institute of Art" ;ondon" &'74" &@ pp." unpublished typescript. &@3 %oring" 9. and .wer" >." +*eport on test performed to determine the optimal concentration of the surfactant Jrvus WA paste for cotton+ in %ridgland" 6." ed." 9reprints of the ;=th Triennial >eeting of the :7?> 7ommittee for 7onservation, %ashington -7, ;22F, pp. 07''1. &@4 .wer" >. and *udolph" *." +*eport on Jrvus WA paste test+" Textile 7onservation Aewsletter 00" 8pring &''0" pp. 0-3. &@5 *eponen" T.2." +The effect of conservation wet cleaning on standard soiled wool fabric: some experimental wor/+ in %ridgland" 6." ed." 9reprints of the ;=th Triennial meeting of the :7?> 7ommittee for 7onservation, %ashington -7, &''1" pp. 10&-4. &@7 ?inn" 9..." )avis" ?.A. and 6ungermann" .." +8tatistical approach to detergency &&&% .ffect of artificially soiled test cloth+" Hournal of the @merican ?il 7hemists' 5ociety @1" 9ay &''4" pp. 1&5-0(. &@' *ut/ows/i" %.6." +An electrophoretic study of the detergency process+" H.?.7.5., April &'47" pp. 045-5&.+ &3( <ramer" 6.6." +.valuation methods for soil removal and soil redeposition. <hapter '+ in <utler" W.?. and )avis" *.<." eds." -etergency Theory and Test >ethods, >art I" 9arcel )e//er" &'53" pp. 101-@&&. &3& .astaugh" G." +8ome experiments comparing the performance of detergent formulations based on anionic and nonionic surfactants under conditions relating to conservation use+ in ?rimstad" :." ed." 9reprints of the <th Triennial >eeting of the :7?> 7ommittee for 7onservation, 5ydney, The ?etty <onservation Institute" 9arina del *ev" &'75" pp. 135-4@. &30 8hebs" W.T." +*adioisotopes Techni!ues in )etergency+ in <utler" W.?. and :issa" .." eds." -etergency/ Theory and Technology, 9arcel )e//er Inc." &'75" pp. &-7'. &31 9ee/" ).9." +9icroscopical studies of detergency: dirt removal from naturally soiled fibres+" Textile 8esearch Hournal 35" &'44" pp. 115-@1. &3@ Wolf" 8.6. and 2ughes" 9.<." +The effects of wet cleaning on dry site archaeological textiles. *esults of a pilot study+ in 9ostprints of the >eeting of the @:7 Textile 5pecialty .roup, AI<" &''0" pp. 5-&@. &33 Jbendorf" 8.:." +8oiling and soil removal as studied by electron microscopy+ m @@T77 Boo( of 9apers, &'75" pp. 05'-7@. &34 Jbendorf" 8.:." +.lectronmicroscopical study of soiling and soil removal+" Textile 7hemist M Co)o%ist 0(" no. 3" 9ay &'77" ;;% 11!15% &35 >radhan" *.9." +Application of scanning electron microscopy to the study of cotton fabric+" Textile :ndustry and Trade Hournal 0(" 9ay-6une &'70" pp. 1-7. &37 <oo/" W.)." %aba/hami" A. and 2illyer" I.." +The cleaning of degraded linen" >art I and >art &&+" The 7onservator 0(" &''4" M:I<" ;ondon" pp. 1-&@. &3' :issa" .." +.valuation of detergency+ in <utler" W.?. and :issa" .." eds." -etergency N Theory and Teclmology, 8urfactant 8cience 8eries" 9arcel )e//er" &'75" pp. 003-4(. &4( 8hashoua" \." +Investigation into the effects of cleaning old" dyedC naturally soiled textiles" by a!ueous immersion+ in %ridgland" 6." ed." 9reprints of the ;=th Triennial >eeting of the :7?> 7ommittee for 7onservation, %ashington -7, &''1" pp. 5&@-0(. &4& %urgess" 2.)." +?e^ permeation chromatography. Mse in estimating the effect of water washing on the long-term stability of cellulosic fibres+ in Geedles" 2.;. and Qeronian" 8.2." eds."

"istoric Textiles and 9aper >aterials/ 7onservation and 7haracterisation, Advanced <hemistry 8eries 0&0" American <hemical 8ociety" &'74" pp. 141-54. &40 2utchins" 6." +The effect of wet cleaning on cotton+" 8eport of the Textile 7onservation .roup F, no. &" 8eptember &'7(" pp. &-@. &41 >radhan" *.9." +8canning electron microscopic 8.9$ study of damage to cotton fabric washed in harsh detergent formulation+" Textile :ndustry and Trade Iournal 0(" Govember-)ecember &'70" pp. 0'-1(. &4@ Wallenborg" I." +Twattunderso/ind av textil+" An examination of some methods for cleaning textiles$" >eddelelser on $onservermg 1" no. 4" &'71" pp. 0&5-1@. &43 ?oli/ov" P.>. and Mstinov" 8.P." +<omplex experimental investigation of the effect of cleaning compositions on the fibres and dyes of museum textiles+ in ?rimstad" :." ed." 9reprints of the <th Triennial >eeting of the :7?> 7ommittee for 7onservation, 5ydtiey, The ?etty <onservation Institute" 9arina del *ev" &'75" pp. 151-5. &44 Asnes" 2." +Wet- and dry-cleaning methods for old textiles+ in 8eggonng vid textil(onservenng idag och i framtiden *Textile 7leaning and 7onservation Today and Tomorrow,, 8eminar" Army 9useum" 8toc/holm" &''1" pp. &1-&4. &45 2ansen" ... and )erelian" 8." +<onservation I. .ffects of wet cleaning on sil/ tapestries+. >useum management and curatorship &(" no. &" &''&" pp. '1-4. &47 9asschelein-:leiner" ;." +;e nettoyage des textiles anciens+" Bulletin :.8.9.@. ?&&&, &'5&0" pp. 0&3-00. &4' )uff" ).?." 8inclair" *.8. and 8tirling" )." +The fastness to washing of some natural dyestuffs on wool+" 5tudies in 7onservation ;;, &'55" pp. &5(-4. &5( American Association of Textile <hemists and <olorists" @@T77 Technical >anual, AAT<<" &'7'" p. 4F4. &5& )aniels" P." +<olour changes of watercolour pigments during deacidification+ in %romelle" G.8. and Thomson" ?." eds." 5cience and Technology in the 5ervice of 7onservation, II<" ;ondon &'70" pp. 44-5(. &50 Pago .." +>roblems encountered during the restoration of a 2ungarian military gala coat+ in Timar-%ala#sy c.. and .astop" )." eds." :nternational 9erspectives on Textil 7onservation, Archetype" ;ondon" &''7" pp. &(@-5. &51 )ir/s" :." +The wet cleaning of an American !uilt+ in >ertegato" ." ed.. 7onservation and 8estoration of Textiles. 9roceedings of the :nternational 7onference, Como ;2<=, <I88TT.ombardy 8ection" &'70" pp. &7@-5. &5@ %rusehus-8charff" A." +8ynthetic dyestuffs for textiles and their fastness to washing+ in %ridgland" 6." ed." 9reprints of the ;;th Triennial >eeting of the :7?> 7ommittee for 7onservation, #yon, 6ames K 6ames" ;ondon &'''" pp. 43@-4(. &53 Jger" %." 3:ast ess to light and washing of direct dves for cellulose textiles+" 5tudies in 7onservation @&" &''4" pp. &0'-13. &54 Thomas" 2." +8urfactants and the environment - an overview+ in :arsa" ).*." ed." :ndustrial @pplication of 5urfactants IP" The *oyal 8ociety of <hemistry" <ambridge" &'''" pp. 01-1'. &55 8chic/" 9.6." +%iodegradation <hapter 0'+ in 8chic/" 9.6." ed." Aonionic 5urfactants, 8urfactant 8cience 8eries &" 9arcel )e//er Inc." &'44" pp. '5&-'3. &57 >otter" 6." -ue to 7 regulations, 5ynperoiiic A may !e !anned in the future on environmental grounds. -iscussing the properties of 5ynperoiiic A that made it so popular and what criteria will influence the choice of a replacement, .ssay submitted to the *<A/PKA Training >rogramme" ;ondon" &''0" unpublished typescript. &5' )aniels" P." +8ynperonic G and G)%+" 7onservation Aews 47" 9arch &'''" p. 4. &7( Wee/s" 6.A." Adams" W.6." ?umev" >.)." 2all" 6.. and Gaylor" <.?." +*is/ assessment of nonylphenol and its ethoxylates in M.8. river water and sediment+ in 9roceedings of the Kth %orld 5urfactants 7ongress, Pol. 1" <...)." &''4" pp. 054-'&. &7& 2ayward" 9. and Allen" *." +Gapthalene+" 7onservation Aews @'" Govember &''0" pp. @(-1.

&70 8wisher" *.)." +<hemical structure and primary biodegradation <hapter 4+ in 8wisher" *.)." ed." 5urfactant Biodegradation, 8urfactant 8cience 8eries 1" 9arcel )e//er" &'5(" pp. 0(1-33. &71 Gaithani" 2.:. and :harbade" %.P" +An overview on the considerations of cleaning of historic textiles+ in 8ingh" T." ed." 7onservation of 7ultural 9roperty in :ndia VPIII-VV" Indian Association for the 8tudy of <onservation of <ultural >ropcrry" &'73-5" pp. 13-@(. &7@ 2illyer" ;." +The cleaning archaeological textiles+ in J+<onnor" 8.A. and %roo/s" 9.9." eds." @rchaeological Textiles ?ccasional 9apers &(" M:I<" &''(" pp. &7-0&. &73 Gagy" :." +)ie Tracht eines vornehmen ungarischen 9adchen aus dem &4. 6ahrhundert+ in @rs -ecorativa 5" 9useum of Applied Arts" &'70" pp. 03-5'. &74 *ice" 6.W." +>rinciples of fragile textile cleaning+ in ;eene" 6..." ed." Textile 7onservation, %utterworths" ;ondon" &'50" pp. 10-50. &75 Dinch" :. and >utnam" ?." 7aring for Textiles, %arrie cv 6en/ins" &'55" pp. @4-7. &77 Dinch" :. and >utnam" ?." The 7are M 9reservation of Textiles, %.T. %atsford ;td." &'73" pp. 4&-5&. &7' 9asschelein-:leiner" ;." +<onservation of very brittle textiles+ in >ertegato" ." ed." 7onservation and restoration of very !rittle textiles. :nternational 7onference Como, ;2<=, <.I.8.8.T.;ombardy 8ection" &'70" pp. 0@3-3(. &'( >ertegato" D." / Tessili. -egrade e Restau%o, Gardmi .ditore" &''1" pp. 4@-5. &'& >ertegato" D." // 8estauro deg)i @razzi, Gardini .ditore" &''4" pp. &5(-7. &'0 ;andi" 8." +Three examples of textile conservation in the Pictoria and Albert 9useum+" 5tudies in 7onservation, Polume &&. Gumber 1" August &'44" pp. &@1-&3'. &'1 ?unilla" ;." +dtrengormg av textilier *%et cleaning of textiles,, 9A Thesis" Institute of <onservation" Mniversity of ?othenburg" &'77" &&@ pp." unpublished typescript. &'@ ?unilla" ;." +<leaning of textiles. )iscussion about research and methods in conservation+ in 2anssen-%auer" D. and :ollansrud" :." eds." Conso)idates and 7onservation >ethods, 9reprints of the Aordis( $onservatorfor!und L:+ 7ongress, G:D-G" &''5. pp. 011-7. &'3 8chneider" 6." +8ome recent textile conservation and restoration wor/ at the 8wiss Gational 9useum Qurich+ in >ertegato" D." ed." 7onservation and 8estoration of Textiles, 9roceedings of the :nternational 7onference, 7omo *+,-, <I88T-;ombardy 8ection" &'70" pp. 05&-3. &'4 Wolf" 8." .wer" >." 2utchms" 6." %uonocore :aldanv" 9. and Appelbaum" %." +.valuating textile treatments: discussing the state-of-the-art+ in 9ostpnnts of the @:7-Textile 5pecialty .roup, ;2th @nnual >eeting, AI<" &''&" pp. &5-03. &'5 %ehar" *." +The cleaning and care of Jriental rugs+" "ali &" Govember &'57" pp. 130-@. &'7 2oward" 8." +An introduction to the wet cleaning of carpets+ in Timar-%ala#sy" A. and .astop" )." eds." :nternational 9erspectives on Textile 7onservation, Archetype" ;ondon" &''7" pp. 04-7. &'' >ata/i A." +*estoration of a &4th century child+s coat +mente+$ belonging to the .sterha#y collection+ in %ridgland" 6." ed." 9reprints of the ;=th Triennial >eeting of the :7?> 7ommittee for 7onservation, %ashington -7, &''1" pp. 1&@-0(. 0(( Di/ioris" 9.A." +The wet cleaning of the sil/ damas/ curtains of the >ort *oyal >arlor at the 2enry Drancis du >ont Winterthur 9useum+ in >ertegato" D." ed." 7onservation and 8estoration of Textiles, 9roceedings of the :nternational 7onference, 7omo ;2<=, <I88T-;ombardy 8ection" &'70" pp. &'7-0(&. 0(& 2istoric *oyal >alaces Textile <onservation 8tudio" Give Oear 8eview ;22;-;22B, pp. 05-0'. 0(0 :eyserhng/" 9." +<onservation and co-operation: treatment of the tablet-woven ?ondar hanging at the <anadian <onservation Institute+ in %ridgland" 6." ed." 9reprints of the ; ?th Triennial >eeting of the :7?> 7ommittee for 7onservation, %ashington -7, &''1" pp. 4''-5(1. 0(1 2aldane" ..-A." +8o that+s why textile conservation has such a big studio: tapestry washing at the PKA+" +M@ 7onservation Hournal 10" &''(" p. 0&.

0(@ 9ar/o" :." %lyth" P. and :andall" 6." +Three methods of handling and washing large tapestry hangings+" The 7onservator 3" &'7&" pp. &-7. 0(3 <ollins" 9." %et 7leaning the "ead)uarters Tent of .eorge %ashington, *eport leaflet" )ivision of Textiles" The Gational 9useum of 2istory and Technology" 8mithsonian Institution" Washington )<" &'45" 1 pp. 0(4 2owell" ). and <arr" <" +Investigation of detergent residues on historic textiles+" unpublished lecture" %et 7leaning 5eminar, Textile <onservation <entre" Winchester" &@ 8eptember 0(((" 0 pp. Author Agnes Timar-%ala#sy !ualified as a chemical engineer. 8he speciali#ed in the study of textiles" paper" leather and the synthetic polymer industry" carrying out research into textile conservation and dye analysis. In &'73 she became a Technical )octor and was awarded a >h.). in &''4. 8he has been employed at the Gational <entre of <onservation / 2ungarian Gational 9useum since &'44. 8ince &'5@ she has been teaching material and conservation science and became 2ead of the Daculty of JbBect <onservation in &'7' and a >rofessor in &''4. Drom &''& she has also been teaching the theory" ethics and history of conservation. 8he has lectured extensively outside 2ungary and has organi#ed a number of international courses on the scientific principles of textile conservation. 8ince &'''-0((( she has been Pice-chairperson of both the I<J9 <ommittee for <onservation and the I<<*J9 <ouncil.