EP1490311A2 - Erhärtungsprodukte für betone und mörtel zur wasserretention während des abbindens und entsprechendes durchführungsverfahren - Google Patents

Erhärtungsprodukte für betone und mörtel zur wasserretention während des abbindens und entsprechendes durchführungsverfahren

Info

Publication number
EP1490311A2
EP1490311A2 EP03745815A EP03745815A EP1490311A2 EP 1490311 A2 EP1490311 A2 EP 1490311A2 EP 03745815 A EP03745815 A EP 03745815A EP 03745815 A EP03745815 A EP 03745815A EP 1490311 A2 EP1490311 A2 EP 1490311A2
Authority
EP
European Patent Office
Prior art keywords
weight
compositions
paraffin
water
emulsion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03745815A
Other languages
English (en)
French (fr)
Inventor
Martin Mosquet
Olivier Malbault
Isabelle Dubois-Brugger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chryso SAS
Original Assignee
Chryso SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chryso SAS filed Critical Chryso SAS
Publication of EP1490311A2 publication Critical patent/EP1490311A2/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/04—Preventing evaporation of the mixing water

Definitions

  • compositions for the treatment of freshly implemented mortar and / or concrete surfaces ensuring the retention of water necessary for their setting and hardening.
  • the invention relates more particularly to curing compositions for mortars and / or concretes freshly used to prevent the evaporation of part of the water involved in their preparation, as necessary for their setting and hardening, compositions comprising in aqueous emulsion at least one paraffin and at least one oil based on ester and / or one oil based on linear and / or cyclic hydrocarbon chains, branched or not, resulting from the crude oil rectification, these various compounds acting in full synergy.
  • the invention also relates to the process for the preparation and implementation of said compositions on the surface of freshly poured mortars and / or concretes.
  • the invention finally relates to the use of said compositions in the form of a layer, deposited on the surface of freshly poured mortars and / or concretes, implemented to ensure the retention of water in mortars and / or concretes at the time of setting and hardening and maintaining a sufficient quantity of water there in order to prevent, or at least limit, the phenomena of shrinkage with the appearance of cracks, and to reserve, for these mortars and / or concretes , the desired characteristics such as, for example, very low shrinkage, good waterproofness, excellent frost resistance and the like.
  • E of technique E of technique
  • a conventional and old treatment to prevent the evaporation of water, consists in maintaining in contact with the surface of mortars and / or freshly poured concrete an atmosphere of humidity as permanent as possible during the setting time, by the creation of a maintained water film or by the implementation of a spongy textile substrate, soaked in water, or by the use of a polymer film unwound on said surface to prevent evaporation, by creating a greenhouse atmosphere between the surface to be protected and the atmosphere.
  • an adherent and protective continuous film is created on the surface of the mortars and / or concretes by depositing therein, by spraying or brushing, a paraffin alone or associated with at least one hydrocarbon resin, in solution in an organic solvent to form a barrier between said surface and the ambient atmosphere and thus prevent the phenomenon of evaporation of the water present in the composition of the mortars and / or concretes from occurring.
  • a continuous and protective film is created on the surface of freshly poured mortars and / or concretes by depositing therein, by spraying or by brushing, an emulsion in water of a paraffin alone or associated with at least one other compound such as a hydrocarbon resin, a hydrocarbon oil and / or a pigmentary filler and / or fatty alcohols and / or fatty acids, to form, early in the setting, barrier between said surface and the ambient atmosphere and thus preventing the phenomenon of evaporation of water occurring in the composition of the mortars and / or concretes from occurring.
  • This emulsion has in common with mortars and concretes the presence of water which makes compatible and particularly interesting this type of anti-evaporation treatment.
  • compositions in emulsion in water intended for the treatment of freshly implemented mortar and / or concrete surfaces the function of which is to prevent the evaporation of water. involved in the formation of said mortars and concretes.
  • a first document (US2, 928, 752) describes aqueous emulsions intended for the protection of the surfaces of mortars and / or concretes during the setting period, then at the beginning of the curing period, to avoid the evaporation of water, these emulsions comprising a paraffin, a reaction product made of ethylene oxide and of unsaturated oleic alcohol, an amino salt of carboxylic acid with long chain C ⁇ 2 to C_, a, a fatty alcohol with long chain C ⁇ 2 to C 2 o and, optionally, a small amount (0 to 10% by weight) of a mineral oil intimately mixed, when it is present, with the molten paraffin to make this paraffin more malleable.
  • compositions whose essential drawback is to be made complex by the number of components which form them, are supposed to be made more adhesive to the surfaces of mortars and / or concretes to be protected from the evaporation of water by the presence of the amine function having an affinity for components of mortars and / or concretes.
  • compositions are intended to be made more adherent to the surfaces of mortars and / or concretes to be protected from the evaporation of water, thanks to the presence of the amino function or of the alkaline compound neutralizing the acid function of saturated and unsaturated fatty acids, this function is innate and this alkaline compound has the advantage of having an affinity for the components of mortars and / or concretes.
  • these protective coating compositions for mortar and / or concrete surfaces to prevent the evaporation of water during setting and hardening have drawbacks which are, for example:
  • compositions with a high reflectance capacity capable of being an aid for reducing the evaporation of water on the surface of mortars and / or concretes during setting and hardening;
  • Another document (US4, 239, 540) describes an aqueous emulsion for protecting the surfaces of freshly poured mortars and / or concretes, to prevent the evaporation of water during the setting and then hardening period, which consists of '' a paraffin (18.2% by weight), a mixture of oils formed from a coconut oil (4.2% by weight), a soybean oil (3.3% by weight), linseed oil (4.2% by weight), stearic acids (3.4% by weight), hexacosanic acid (1.6% by weight), water (62.5% by weight) and an ester of ethyl and cyanuric acid (2.6% by weight) as an emulsifying agent.
  • This aqueous emulsion with a very specific and very narrow composition which could seem advantageous for the treatment of prevention against the evaporation of water from the surfaces of mortars and / or concretes at the time of setting and hardening, is in reality unusable. both the results stated show its very low capacity to be a water retentive (0.027 to 0.038 g of water / cm 2 ).
  • this aqueous emulsion contains organic acids whose acid function:
  • Another document discloses a method of preparing an emulsion intended for the treatment of curing of surfaces of freshly poured mortars and / or concretes to prevent the evaporation of the water present on the surface of said mortars and / or concretes ' during the setting period and the hardening period.
  • This emulsion is formed from hydrocarbon resin, paraffin, emulsifying agents obtained from fatty acids and morpholine.
  • pigments such as Ti0 2 and / or mineral filler such as CaC0 3 is also disclosed.
  • this emulsion has the disadvantage of being composed of solids at room temperature, that is to say paraffin and hydrocarbon resin in the solid state, making the preparation of the emulsion difficult and leading to an emulsion which can be unstable and can be used as a protective film against the evaporation of surface water from freshly poured mortars and / or concretes which is rather disappointing: the capacity of this emulsion to prevent loss of water by evaporation appears insufficient even though this emulsion would contain a pigment to increase the reflectance and, therefore, to try to increase its efficiency.
  • Another document (FR2691962) describes aqueous emulsions of paraffin and natural or synthetic hydrocarbon resins, in particular pine resins which are intended to be applied to freshly poured mortar and / or concrete surfaces, to limit the evaporation of water during the setting period and the start of hardening.
  • the various objects assigned to the invention appear to be the creation of organic compositions which are aqueous emulsions endowed with the essential characteristics necessary and sought for them to be applied to mortar surfaces and / or freshly poured concrete and, once applied, it limits and, preferably, prevents the evaporation of water, absolutely necessary for their setting and hardening.
  • aqueous emulsions according to the invention Among the essential characteristics assigned to the aqueous emulsions according to the invention, some of the inputs are specified by way of illustration.
  • the aqueous emulsions according to the invention :
  • - may not contain compounds capable of deactivating the mortars and / or the concrete receiving them;
  • - must be free of carcinogenic compounds such as, in particular, benzene, toluene, xylene; - must allow, after their degradation, good adhesion for the finishing materials applied to the treated surfaces.
  • the aqueous emulsions intended to be applied to freshly poured mortar and / or concrete surfaces to prevent the evaporation of water from the start of setting at least partially eliminate the drawbacks manifested in the state of the technique and bring, in addition, substantial improvements that do not exist in the means described to date to make the emulsions particularly effective in the role assigned to them.
  • compositions intended to be applied to freshly poured mortar and / or concrete surfaces, before the start of setting, to prevent the evaporation of the water necessary for their setting and their hardening are characterized in that, in order to make them synergistic with regard to water retention, they are composed, in the form of aqueous emulsions:
  • At least one paraffin of petroleum or synthetic origin containing, as a mixture, aliphatic saturated and unsaturated hydrocarbons of general formulas CnH 2n +2 and CnH 2n for which n is at least 30 and whose point of melting is between 40 ° C and 75 ° C;
  • compositions according to the invention intended to be applied to freshly poured mortar and / or concrete surfaces before the start of setting to prevent the evaporation of the water necessary for setting them, are:
  • the compositions intended, by their presence, to prevent the evaporation of water from freshly poured mortars and / or concretes are aqueous paraffin emulsions.
  • an emulsion is, by definition, a dispersion of a liquid compound or made liquid in another liquid compound.
  • the paraffinic compound, said component (a) which, at an ambient temperature, a solid compound is immiscible with water, is made liquid by a slight rise in temperature and simultaneously dispersed in water brought to a suitable temperature for the formation of an emulsion under strong agitation.
  • the paraffinic compound may already be in the form of an aqueous emulsion sold and be used in this state for the preparation of the compositions according to the invention.
  • the paraffin used in the context of the invention for the production of the abovementioned emulsion, is chosen from the group consisting of alkanes and / or alkenes, taken alone or as a mixture, which are saturated hydrocarbons and / or unsaturated, of petroleum or synthetic origin, of general formulas CnH 2n + 2 and CnH 2n for which n is at least equal to 30 and is preferably between 30 ⁇ n ⁇ 120 and whose melting point is between 40 ° C and 75 ° C and preferably between 50 ° C and 70 ° C.
  • the density of said paraffin is between 0.85 and 0.95 and preferably between 0.88 and 0, 92.
  • an emulsifying agent facilitating the stability 1 emulsion can be introduced into said emulsion, said agent being capillairement active and placing, as a result of an adsorption phenomenon, in • the parting surface micro-droplets of paraffin and water by wrapping an interfacial film.
  • Such an emulsifying agent can be of anionic and / or nonionic nature. It can be chosen from well-known emulsifying products such as fatty acids, Cs to C 2 2 neutralized by an amine, in particular triethanolamine, sulfonated, phosphonated compounds; fatty alcohols, sorbitan esters, ethylene oxide-propylene oxide copolymers, or the like.
  • emulsifying agents are, for example, marketed by SEPPIC under the name of Simulsol, Montane, Montanox and by LAMBERT-RIVIERE under the name of Syntopon.
  • Paraffin emulsions in water whose paraffin meets the above characteristics, are marketed, for example, by Exxon-Mobil Oil under the brand names Mobilcer 115, Mobilcer 730, Mobilcer C, Prowax 397, Mobil ax 2370 or even by Suddentsche Emusions Chemie under the brand names Wukonil KN 50, Wukonil LP 50, Wukonil LP 38 or by Michelman under the brand name ME91240E.
  • compositions according to the invention also contain at least one hydrocarbon-based oil, called component (b), of petroleum origin of aliphatic and / or naphthenic type and, in the latter case, originating from the series of cyclopentanes and cyclohexanes, which are hydrocarbons, present alone or in mixtures, saturated and / or unsaturated, of general formulas CnH 2n + 2 and / or ' CnH 2n for which n is less than 30 and is preferably between 10 and 25, these hydrocarbon oils being in a liquid state at room temperature.
  • component (b) of petroleum origin of aliphatic and / or naphthenic type and, in the latter case, originating from the series of cyclopentanes and cyclohexanes, which are hydrocarbons, present alone or in mixtures, saturated and / or unsaturated, of general formulas CnH 2n + 2 and / or ' CnH 2n for which n is less than 30 and is preferably between 10 and 25, these hydro
  • All these oils have, under normal conditions of temperature and pressure, a kinematic viscosity between 5 and 500 mm 2 / s and a density between 0.83 and 0.97.
  • hydrocarbon-based oil of aliphatic and / or naphthenic origin it is possible to indicate, by way of example, Neutral oil, sold by Exxon-Mobil, which has a kinematic viscosity equal to 20 mm 2 / s, or HMVIP 30, HVI 65 oils sold by Shell, 60 Neutral, 80 Neutral, 150 Neutral sold by Exxon-Mobil.
  • compositions according to the invention also contain, associated with or in replacement of component (b), at least one oil liquid at room temperature which is formed from an ester resulting from the condensation reaction of a saturated fatty acid and / or unsaturated with a mono, di or trihydric alcohol, constituting component (c).
  • the fatty acids used in the formation of the ester according to the invention are hydrocarbon-based, saturated and / or unsaturated, branched or non-branched, compounds originating from the hydrogenation of oils and fatty substances, preferably carrying only one carboxylic acid function. . They are generally chosen, for example, from the group consisting of C 8 to C 2 fatty acids.
  • r such as, for example, caprylic, capric, lauric, myristic, palmitic, stearic, arachidic, behenic, lignoceric, palmitoleic, oleic, gadaleic, erucic, linoleic, linolenic, isolinolenic acid.
  • the alcohols used in the formation of the ester according to the invention are hydrocarbon compounds comprising one, two or three alcohol functions from C 2 to C 2 o-
  • These alcohols can be chosen from the group consisting of alkanols and / or alkenols such as, for example, ethanol, propanol, butanol, pentanol, stearic alcohol, oleic alcohol when it is a question of using a monohydric alcohol, in the group constituted, for example, by propane diol, butane diol, pentane diol, hexane diol, heptane diol, octane diol, nonane diol, decane diol, undecane diol and dodecane diol and other dihydroxyalkanes or alkenes, when it comes to using a dihydric alcohol, and / or in the group consisting of glycerol, butane triol, pentane
  • compositions according to the invention produced by means of components (a), (b) or (c) that are:
  • paraffins of petroleum or synthetic origin containing a mixture of saturated and / or unsaturated hydrocarbons of general formula CnH 2n + 2 and / or CnH 2n with n>30;
  • synergistic compositions intended to be applied on freshly poured mortar and / or concrete surfaces, before the start of setting, to prevent the evaporation necessary for their setting and their hardening, the synergistic character of which is asserted through their ability to prevent the evaporation of water infinitely better than emulsions of paraffins alone or oils alone.
  • - component (a) or paraffin from 2% to 90% by weight, preferably from 5% to 60% by weight, very preferably from 5% to 40% by weight;
  • - component (b) or hydrocarbon oil from 5% to 90% by weight, preferably from 8% to 40% by weight, very preferably from 9% to 30% by weight;
  • - component (c) or oil formed from at least one ester from 5% to 90% by weight, preferably from 10% to 50% by weight, very preferably from 15% to 40% by weight;
  • the weight ratio of dry active material of the combination of oils and paraffin present in the aqueous emulsions of the compositions according to the invention must be at least equal to 0.25, can preferably be at least equal to 0.63 and can vary very preferably between 0.64 and 9.
  • compositions according to the invention in the form of aqueous emulsions, have a dry matter content which can vary, in general, from 10% to 60% by weight, but preferably from 30% to 50% by weight.
  • compositions in the form of aqueous emulsions are used by spraying onto the surfaces to be protected, the payload deposited per unit of surface being between 50 g / m 2 and 150 g / m 2 to achieve total protection, ie ie an absence of evaporation of said surfaces.
  • compositions according to the invention which are aqueous emulsions, are stable on storage, even for prolonged periods.
  • compositions according to the invention when used, they prove to be very effective because, in contrast to the compositions of the state of the art, they require a quantity of active dry matter deposited per m 2 to protect infinitely weaker, thus making them both very effective and very economical.
  • the invention also relates to a process for the preparation of compositions for protecting against the evaporation of water from freshly poured mortar and / or concrete surfaces, which comprises the successive steps of introducing the various components into a very heavily subjected preparation area stirring, the contents of which can be heated and / or cooled, these steps being: i) the introduction, according to the calculated quantity, of water, necessary for the creation of the emulsion, then optionally that of an emulsifying agent in said zone, this first mixture being subjected to strong stirring for the time necessary to obtaining a homogeneous medium;
  • compositions according to the invention were prepared in the form of an aqueous emulsion, formed from:
  • Mobilcer 115 (registered trademark), sold by the company MOBIL in the form of an aqueous emulsion at 45% by weight of dry extract;
  • - oil of type (c) which is a fatty acid ester of triglyceride, resulting from the esterification of a mixture of acids (TUNGOIL oil) which are, at 80% by weight, acid eléostéarique (in Cig with 3 unsaturations), at a rate of 1% of palmitic acid (in Cie) and at a rate of 19% of linoleic, linolenic and oleic acids (in C ⁇ 8 ) by glycerol;
  • TUNGOIL oil acid eléostéarique
  • the method of preparation was as follows
  • the quantity of water necessary for producing the composition according to the invention is first introduced into a suitable reactor by the formation of an aqueous emulsion.
  • the amount of water initially introduced takes account of the amount of water contained in the aqueous paraffin emulsion.
  • an emulsifying agent for example Montanox 85 (registered trademark) sold by the company SEPPIC.
  • the water initially introduced is subjected, whether or not it contains a dispersing agent, to significant agitation by a TURAX agitator rotating at 20,000 revolutions / minute.
  • the oil of type (c) is introduced into the aqueous volume, forming a mixture maintained under vigorous stirring for five minutes, to form the "oil in water” emulsion.
  • the mixture of emulsions formed is subjected, for at most 90 minutes, to gentle agitation, the speed of rotation of the TURAX being maintained at 5000 revolutions / minute.
  • the composition according to the invention is ready to be used by spraying, at a rate of 60 g / m 2 of a composition according to the invention containing 50% by weight of dry extract .
  • the percentage by weight of water, present in the composition according to the invention is the cumulative amount of water present in the Mobilcer 115 emulsion (at 45% by weight of dry extract), and water introduced as a supplement, the percentage by weight of paraffin being thus expressed as a percentage by weight of dry extract, as well as the percentage by weight of the oil based on esters used.
  • aqueous emulsion compositions were prepared, two of them (9, 10) containing the same oil in water emulsion as that used in the eight formulas of the invention, the other two (11, 12) containing the same paraffin emulsion in water as that used in the eight formulas of the invention.
  • Tests on the use of said compositions have been carried out in the form of a sprayed layer for each of them, deposited on the surface of freshly poured mortars and / or concretes, used to ensure water retention at the within said mortars and / or concretes at the time of setting, then of their hardening.
  • a phenomenon of maximization of the protection of the treated surfaces occurs when the ratio of the percentages by weight of oil to the percentages by weight of dry paraffin extract, in the compositions according to the invention, is very preferably between 0, 64 and 9;
  • compositions according to the invention were prepared in the form of an aqueous emulsion, formed from:
  • Mobilcer 115 (registered trademark), sold by the company MOBIL in the form of an aqueous emulsion at 45% by weight of dry extract;
  • the percentage by weight of water, present in the composition according to the invention is the sum of the water present in the Mobilcer 115 emulsion (at 45% by weight of dry extract), the percentage by weight of paraffin being thus expressed as a percentage by weight of dry extract, as well as the paraffinic oil used.
  • compositions 13 to 19 according to the invention have received an emulsifying agent which is a nonionic agent, sorbitan ester, having 85 ethylene oxide units, sold under the trademark MONTANOX 85 by the company SEPPIC.
  • an emulsifying agent which is a nonionic agent, sorbitan ester, having 85 ethylene oxide units, sold under the trademark MONTANOX 85 by the company SEPPIC.
  • compositions in aqueous emulsion were prepared, two of them (20, 21) containing the same oil in emulsion in water as that used in the seven formulas of the invention, the other two (22, 23) containing the same paraffin emulsion in water as that used in the seven formulas of the invention.
  • Tests on the use of said compositions have been carried out in the form of a sprayed layer for each of them, deposited on the surface of freshly poured mortars and / or concretes, used to ensure water retention at the within said mortars and / or concretes at the time of setting, then of their hardening.
  • a phenomenon of maximization of the protection of the treated surfaces occurs when the ratio of the percentages by weight of oil to the percentages by weight of paraffin dry extract, in the compositions according to the invention, is very preferably between 0 , 64 and 9;

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Aftertreatments Of Artificial And Natural Stones (AREA)
  • Paints Or Removers (AREA)
  • Colloid Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
EP03745815A 2002-04-04 2003-04-03 Erhärtungsprodukte für betone und mörtel zur wasserretention während des abbindens und entsprechendes durchführungsverfahren Withdrawn EP1490311A2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0204208A FR2838120B1 (fr) 2002-04-04 2002-04-04 Compositions de cure de mortiers ou betons assurant la retention d'eau(pendant la prise) et procede de mise en oeuvre
FR0204208 2002-04-04
PCT/FR2003/001046 WO2003084897A2 (fr) 2002-04-04 2003-04-03 Compositions de cure de mortiers ou betons assurant la retention d'eau (pendant la prise) et procede de mise en oeuvre

Publications (1)

Publication Number Publication Date
EP1490311A2 true EP1490311A2 (de) 2004-12-29

Family

ID=28052110

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03745815A Withdrawn EP1490311A2 (de) 2002-04-04 2003-04-03 Erhärtungsprodukte für betone und mörtel zur wasserretention während des abbindens und entsprechendes durchführungsverfahren

Country Status (7)

Country Link
US (2) US20050223948A1 (de)
EP (1) EP1490311A2 (de)
AU (1) AU2003246770A1 (de)
CA (1) CA2480981C (de)
FR (1) FR2838120B1 (de)
WO (1) WO2003084897A2 (de)
ZA (1) ZA200407975B (de)

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CN109251664A (zh) * 2018-08-02 2019-01-22 湖南林邑新能源有限公司 一种环保防水桐油及其制备方法

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JP5889058B2 (ja) * 2012-03-15 2016-03-22 太平洋マテリアル株式会社 セメント系硬化体及びセメントモルタル又はコンクリートの養生方法
FR3012136B1 (fr) * 2013-10-21 2019-04-26 Chryso Composition de cure pour composition hydraulique assurant une adherence renforcee
FR3035659B1 (fr) * 2015-04-28 2019-11-01 Coreva Technologies Utilisation d'une composition comprenant un mono- a tetra- alkylenate en c7-c15 de mono- a tetra- (trialkanol en c3-c6) comme auxiliaire de mise en œuvre de produits bitumineux et/ou de beton
US12479125B2 (en) 2022-02-15 2025-11-25 Titan America LLC Concrete composition suitable for 3-D printing and a method for 3-D printing of multiple layers of concrete

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Also Published As

Publication number Publication date
CA2480981C (fr) 2010-11-23
ZA200407975B (en) 2006-06-28
WO2003084897A2 (fr) 2003-10-16
CA2480981A1 (fr) 2003-10-16
WO2003084897A3 (fr) 2004-04-01
US20050223948A1 (en) 2005-10-13
FR2838120A1 (fr) 2003-10-10
FR2838120B1 (fr) 2004-06-11
AU2003246770A1 (en) 2003-10-20
US20100129671A1 (en) 2010-05-27
US8092589B2 (en) 2012-01-10
AU2003246770A8 (en) 2003-10-20

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