EP1421165A1 - Method for treating a surface with a treating gel and treating gel - Google Patents

Method for treating a surface with a treating gel and treating gel

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Publication number
EP1421165A1
EP1421165A1 EP20020760387 EP02760387A EP1421165A1 EP 1421165 A1 EP1421165 A1 EP 1421165A1 EP 20020760387 EP20020760387 EP 20020760387 EP 02760387 A EP02760387 A EP 02760387A EP 1421165 A1 EP1421165 A1 EP 1421165A1
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EP
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Patent type
Prior art keywords
gel
treatment
silica
surface
weight
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.)
Granted
Application number
EP20020760387
Other languages
German (de)
French (fr)
Other versions
EP1421165B1 (en )
Inventor
Sylvain Faure
Bruno Fournel
Paul Fuentes
Yvan Lallot
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.)
Areva NC
Original Assignee
Areva NC
Commissariat a l'Energie Atomique et aux Energies Alternatives
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Classifications

    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/001Decontamination of contaminated objects, apparatus, clothes, food; Preventing contamination thereof
    • G21F9/002Decontamination of the surface of objects with chemical or electrochemical processes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/0008Detergent materials characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003Colloidal solutions, e.g. gels; Thixotropic solutions; Pastes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/042Acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz, glass beads
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23GCLEANING OR DEGREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/025Cleaning or pickling metallic material with solutions or molten salts with acid solutions acidic pickling pastes
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23GCLEANING OR DEGREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions

Abstract

The invention concerns a method for treating a surface with a gel, and a treating gel. The treatment may for example consist of a decontamination, stripping or degreasing treatment of a surface. The method comprises the following successive steps: applying the treating gel on the surface to be treated; maintaining the treating gel on the surface to be treated at a temperature and relative humidity such that the gel dries when breaking up and that it has sufficient time to treat the surface before forming a dry and solid residue; and eliminating the dry and solid residue from the treated surface, by suction or brushing. The gel comprises a viscosifier, a treating agent and optionally an oxidising agent.

Description

PROCESS FOR TREATING A SURFACE TREATMENT GEL, GEL AND TREATMENT.

DESCRIPTION

TECHNICAL AREA

The present invention relates to a method of treating a surface with a gel, as well as a treatment gel usable in such a method. Treatment may be for example a decontamination treatment by radioactive or organic example, a pickling treatment or a degreasing treatment of a surface.

It can be used on all kinds of surfaces to be treated, such as metal surfaces, plastic surfaces, glassy material surfaces, etc ..

STATE OF PRIOR ART The gels of the prior art do not dry or several tens of hours and must all be removed after a few hours by rinsing with water. Rinsing also possible to interrupt the action of frost on the wall and to control the duration of action of frost.

Rinsing present one drawback of generating liquid effluents of the order of 10 L of water per kg of gel used. This effluent decontamination when it comes to radioactive decontamination are treated in existing facilities for processing of nuclear material. This therefore requires extensive studies on the management of these effluents and their vis-à-vis the impact of facilities processing circuits. Furthermore, such gels that must be rinsed can not be used to treat surfaces that installation should not be flooded.

DISCLOSURE OF INVENTION

The present invention specifically aims to provide a method of treating a surface by a gel, and a gel useful treatment in such a process, which overcomes the aforementioned drawbacks of the prior art.

The processing method comprises in this order the following steps: - application of the treatment gel on the surface to be treated, maintaining the treatment gel on the surface to be treated at a temperature and relative humidity such that the gel dries and has the time to treat the surface before forming a dry and solid residue, and removing the dry and solid residue from the treated surface.

Preferably, according to the invention, the dry gel fracturing.

The interests of such treatment, said gel "drawable" compared to treatment of the prior art are many. First, it has the advantages of treatment with gel. For example, it avoids at a decontamination "on site" of radioactive installations, projections of aqueous solutions producing large amounts of radioactive effluents for a limited effectiveness because of low contact time with the parts.

Then it avoids the conventional operation gel rinsing with water or other liquid and thus produces no liquid effluent to be treated subsequently. This results in a decrease in the amount of effluents and a simplification in terms of global example decontamination treatment process. According to the invention, the treatment gel is advantageously composed of a colloidal solution comprising:

- 5 to 25% by weight of a thickening agent inorganic or a mixture of inorganic viscosing agents based on the weight of the gel,

0.1 to 7 mol / 1, preferably from 0.5 to 4 mol / 1, of an active treatment agent, and optionally from 0.05 to 1 mol / 1 of an oxidizing agent with a normal potential redox E 0 larger than 1.4 V in a strong acid medium or of the reduced form of this oxidizing agent.

The concentrations are expressed in moles per liter of gel in the present text. The inorganic thickening agent, or inorganic, may for example be based on silica or of a mixture of silicas. Preferably, according to the invention, the silica is at a concentration of 5 to 15% by weight of the gel to ensure drying of the gel at a temperature between 20 ° C and 30 ° C and relative humidity between 20 and 70% by average in 2 to 5 hours. This silica may be hydrophilic, hydrophobic, acidic or basic as Tixosil 73 (trademark) marketed by Rhodia.

Among the acid silicas, mention may be made fumed silicas "Cab-O-Sil" M5, H5 or EH5 (trademark) marketed by Cabot and fumed silicas marketed by Degussa under 1 'ppellation AEROSIL (trademark of business) . Of the fumed silicas, AEROSIL 380 silica is preferred (trademark) of a surface area of 380 m 2 / g which offers the maximum viscosity-modifying properties for a minimum mineral filler.

The silica used may also be called a precipitated silica obtained for example by wet by mixing a sodium silicate solution and an acid. Preferred precipitated silicas are sold by Degussa under the name Sipernat 22 LS and FK 310 (trademarks). Advantageously, according to the invention, the thickening agent is a mixture of both types of the aforementioned silicas, pyrogenic and precipitated. In this case, the mixing of silica is preferably at a concentration of 5 to 10% by weight of the gel to provide a drying at a temperature of gel between 20 ° C and 30 ° C and relative humidity between 20 and 70% by average in 2 to 5 hours. Indeed, such a mixture influence unexpectedly drying the gel and the particle size of the obtained residue. Indeed, the dry gel is in the form of controlled particle size ranging from 0.1 to 2 mm thanks to the above compositions of the present invention.

For example, adding 0.5% by weight of a precipitated silica FK 310 (trademarks) in an 8% gel of silica Aerosil 380 (trade marks) increases the particle size of the dry residue and leads to prunings millimeter facilitating the removal, or retrieval, by brushing or vacuuming. The mineral thickening agent may also be, for example alumina Al 2 0 3, obtained for example by hydrolysis at high temperature. Preferably, the alumina is at a concentration of 10 to 25% by weight in the gel to ensure drying of the gel at a temperature between 20 ° C and 30 ° C and relative humidity between 20 and 70% within 2 to 3 hours. Examples include the product sold by Degussa under the trade name "Alumina C".

The active treatment agent may be an acid or mixture of acids, preferably selected from hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid. The acid is preferably present at a concentration of 0.1 to 7 mol / 1, more preferably from 0.5 to 4 mol / 1, to ensure drying of the gel at a temperature between 20 ° C and 30 ° C and relative humidity between 20 and 70% on average in 2 to 5 hours.

For this type of acid gel, inorganic thickening agent is preferably silica or a mixture of silicas. Treatment gel according to the invention may also contain as an active treatment agent a base preferably an inorganic base selected preferably from sodium hydroxide, potassium hydroxide or mixtures thereof.

The base is preferably present at a concentration of less than 2 mol / 1, preferably between 0.5 and 2 mole / l, more preferably between 1 and 2 mol / 1 to ensure drying of the gel at a temperature between 20 ° C and 30 ° C and relative humidity between 20 and 70% on average in 2 to 5 hours

For this type of alkaline gel, the inorganic thickening agent is preferably one alumina.

Finally, the gel of the invention may contain an oxidizing agent with a standard oxidation-reduction potential greater than 1400 mV in a strong acid medium, that is to say an oxidizing power higher than that of permanganate. By way of example, such oxidizing agents can be Ce (IV), Co (III) and Ag (II).

Oxidizing agents, including the cerium IV is preferred, are generally associated with a mineral acid such as nitric acid preferably at a moderate concentration of less than 2 mol / 1 and allowing rapid drying of the gel. Cerium is generally introduced in the form of cerium (IV) nitrate electrogenerated Ce (N0 3) 4 or 1 'hexanitrato cerate of diammonium (NH 4) 2 Ce (N0 3) 6.

Thus a typical example of oxidizing decontamination gel according to the invention is composed of a colloidal solution comprising 0.1 to 0.5 mol / 1 of Ce (N0 3) 4 or (NH 4) 2 Ce (N0 3) 6 / 0.5 to 2 mol / 1 of nitric acid and from 5 to 15% by weight of silica.

The gels of the invention can be easily prepared at room temperature by adding to an aqueous solution of the inorganic gelling agent which preferably has a high surface area, for example greater than 100 m 2 / g. A viscosity at least equal to 350 mPa.s and a recovery time of viscosity less than one second are preferred so that the gel can be sprayed at a distance or not, on the surface to be treated without dripping.

The objective achieved by the present invention is also to provide action time gels controlled by a fast drying time, sufficient to ensure the treatment of the surface, usually between 2 and 5 pm, and even between 2 and 3 hours, at a temperature between 20 ° C and 30 ° C and average relative humidity between 20 and 70%.

Moreover, because the gels of the invention comprise a thickening agent or preferably a mixture of viscosifying agents and an active decontamination agent to the above concentrations, the gel drying leads to a dry residue having an ability to detach easily support. Thus, no rinsing with water is required and the method thus generates no secondary effluent.

The gels of the present invention can be generally described as colloidal solutions comprising one or more thickening agents generally inorganic, such as alumina or silica, and an active treatment agent, for example an acid, a base, an oxidizing agent , a reducing agent or a mixture thereof, which is selected in particular depending on the nature of the treatment and the surface to be treated. Thus, for a treatment consisting in the removal of loose contamination, in the form of fats, on stainless steel surfaces and ferritic, an alkaline gel having degreasing properties may be used. The elimination of a hot and cold fixed contamination on a stainless steel surface may be by means of an oxidizing gel. The dissolution of oxide layers can be done by means of a reducing gel which will be preferably used in addition to the oxidizing gel and alternately.

Finally, a fixed contamination cold on a ferritic steel can be eliminated for example by means of an acid gel.

The gel may be applied to the surface to be treated by conventional methods such as by gun spraying or by means of a brush, for example a brush to be decontaminated.

For spray application of gel on the surface to be treated, the viscous colloidal solution can for example be conveyed via a low pressure pump (<7 bar) and the gel jet bursting on the surface can be obtained with a flat jet nozzle or round jet. The sufficiently short viscosity recovery time enables the sprayed gel to adhere to the wall. The amounts of gel deposited on the surface to be treated are generally from 100 to 2000 g / m 2, preferably 100 to 1000 g / m 2, more preferably 300 to 700 g / m 2. They influence the gel drying time. The gel drying time of the present invention depends primarily on its composition in the concentration ranges defined above. It is generally between 2 and 5 hours, more particularly between 2 and 3 hours, at a temperature between 20 ° C and 30 ° C and average relative humidity between 20 and 70%.

The dry residue obtained after drying can be removed easily, for example by brushing and / or aspiration, but also by gas jet, for example compressed air.

It is evident that the treatment of the surface may be renewed every time with the same gel or with gels of different nature in the different successive steps, each step comprising applying the gel, keeping the gel on the surface for the surface treatment and drying, and removal of the dry residue obtained.

The present invention applies generally to the treatment, for example decontamination of metal surfaces, important or not, which are not necessarily horizontal, but may be inclined or vertical same.

For surface treatment of any treatment means for cleaning, decontaminating or etching said surface. This may be for example a processing radioactive decontamination or organic (e.g., removal of microorganisms, parasites etc ..), a pickling treatment to remove oxides or to a degreasing treatment of a surface. The present invention can be used to treat a variety of surfaces such as metal surfaces, plastic surfaces, glassy material surfaces etc ..

Those skilled in the art will adapt the above compositions of the gels of the present invention following the surface to be treated and the treatment to be performed.

The present invention can advantageously be used for example in the field of nuclear to decontaminate tanks, ventilation ducts, storage pools, glove boxes, etc. It can be used both as part of the periodic maintenance of existing facilities, as sanitation facilities.

Indeed, it reduces the amount of effluent produced during the treatment of the aforementioned elements.

It also finds application in the treatment of installations in which the liquid feed is prohibited. An example of such an application is the decontamination of nuclear facilities ventilation ducts.

The present invention therefore also relates to an installation decontamination process.

According to the invention, the decontamination method may comprise a dedusting installation to be treated, followed by treatment of the facility by means of a processing method according to the present invention.

Dedusting installation to be treated may be achieved for example by brushing, blowing or aspiration of dust to remove non-fixed solid contamination. This pretreatment can be done for example on stainless steel ventilation channels nuclear facilities which contain large amounts of dust.

The treatment method of the present invention can then be used by applying one or more gel passes from one invention to remove contamination attached at the inner walls of the ducts. The gels dry completely after acting on the surface and is easily removed from the wall by suction.

Other features and advantages of the invention will become apparent in the following examples, with reference to the accompanying drawings, given in an illustrative and not restrictive.

BRIEF DESCRIPTION OF FIGURES

Figure 1 illustrates drying charts of a gel according to the present invention at 30 ° C depending on the relative humidity, this gel having a formulation Aerosil 380 (trade name) + 8% HN0 3 July M. - the 2 shows graphs drying of a gel of the present invention at 25 ° C depending on the relative humidity, this gel having a formulation Aerosil 380 (trade name) + 8% HN0 3 7 M (on the curve -x-: T: 25 ° C - H 2: 42% only Si038).

3 shows charts of drying of a gel of the present invention at 20 ° C depending on the relative humidity, this gel having a formulation Aerosil 380 (trade mark) 8% HN0 3 + 7 M.

4 shows charts of drying of a gel of the present invention at 20 ° C and 40% relative humidity as a function of the amount of gel applied on a surface, said gel having a formulation

Aerosil 380 (trade mark) 8% + HN0 July 3 M.

Figure 5 is a graph showing the influence of moisture content on the kinetics of drying at different temperatures for drying a gel according to the invention, this gel having a formulation Aerosil

380 (trademark) 8% + HN0 July 3 M.

Figure 6 is a graph showing the influence of temperature on drying rate of a gel according to the invention at 42% relative humidity, this gel having a formulation Aerosil

380 (trademark) 8% + HN0 July 3 M.

Figure 7 shows four photographs showing dry residues gels obtained with the mixture Aerosil 380 (trade name) and 8% and FK310

(Tradename) 0.5% one hand and the mixture

Aerosil 380 (trade name) and 8% FK310 (trade mark) 1% on the other hand to two drying methods. Figure 8 is a graph showing the weight loss of two alumina gels at 2.5 and 5 mol / 1 of sodium hydroxide as a function of time (M = mass and t = time). In these figures, Te represents the evaporation rate in percentage of the initial amount of solvent, ts: minutes drying time, T: drying temperature for each curve in ° C, Hr and the relative humidity during the various trials in percentage.

EXAMPLES

example 1

Of a silica gel drying properties Aerosil 380, fumed silica with a large specific surface area of 380 m 2 / g are studied in this example.

Preliminary tests performed by the inventors have shown that nitric concentrated medium 7 M, the use of a silica-based formulation pyrogenic, for example AEROSIL 380 Type (trademark) at a concentration of between 8 and 10% by weight makes it possible to obtain dry residues which are easily removed after a few hours (between 2 and 5 hours). Thus, the contact time is sufficient to treat a surface. A content of about 8% by weight of silica was therefore selected by the inventors.

The amount of gel deposited on the surface had only a slight influence on the drying characteristics and especially on the ability to detachment. Different amounts of gel from 0.1 to 2 Kg of gel per m 2 were deposited on the surfaces. The quantities of 0.3 kg.m "2 to 0.7 kg.m" about 2 are preferred.

The drying conditions are the most important parameters in the process of the present invention. Among them, there is the drying temperature and the humidity of the drying air. The existence of a convective current is also important. The influence of these parameters was quantitatively appreciated by plotting drying abaci.

The temperature range which is used is 20 ° C to 30 ° C and the relative humidity of the drying area 20% air at 70% relative humidity being defined as the vapor pressure ratio of water at a given temperature at the vapor pressure of water at the same temperature.

Stainless steel parts are 304L new gelled. The amount of gel deposited is 0.5 kg.m "2 (± 5%) for the following tests when this is not specified.

The silicas are premixed beaker cylindrical tours.min 800 -1 using a propeller stirrer to ensure intimate mixing of the silica. When preparing the gel was stirred at 500 tours.min "1 by the same stirring system.

The coated samples are placed in a climate chamber with controlled temperature and humidity. The climatic chamber is trademark of KBF and volume to 115 liters. The humidity control is provided by injection of steam generated by passing an electric current through the humidifier. The speed of the current convective to the sample surface can be regarded as identical for all cases and very low intensity. The mass of the coating over time is followed for each combination of temperature / set humidity.

1) INFLUENCE OF TEMPERATURE

For three temperatures 30 ° C, 25 ° C and 20 ° C the graphs shown respectively in Figures 1 to 3 have been plotted for several values ​​of the relative humidity.

The curves corresponding to the graphs 30 ° C are shown in Figure 1. The curves in this figure show a linear portion corresponding to the phase rate constant drying. The drying rate is even slower than the humidity is high which is consistent. For low humidity (20% and 35%) is noted the appearance of a bearing from about 200 minutes. This plateau corresponds to 100% solvent evaporated indicating that the decreasing rate drying phase is almost nonexistent. It follows that the gel is totally dry after about three hours when the humidity is less than 35%. However, for values ​​above the level is not reached after the time of experience. It can be obtained by extrapolation of the initial drying phase at constant speed. Under these conditions, we find that in the absence of convection current, a humidity of 50% leads to an extrapolated drying time of 8 hours which is compatible with a decontamination operation. A relative humidity greater than 70% in this case leads to excessive drying times. The curves corresponding to abaci at 25 ° C are presented in Figure 2. The test held at 70% relative humidity was deleted account longer drying times observed at 30 ° C.

The resulting curves have the same shape as 30 ° C. However, the drying times are extended. Total drying is achieved at 35% humidity over a period of about 5 hours. Given the test performed at 30 ° C is determined by extrapolation with a relative humidity of 20% total drying time for this value to 25 ° C is between 3 hours and 5 hours. At 50% moisture content the total drying time is extrapolated 9 hours which is acceptable in a treatment of a surface process.

Thanks to the following tests, it was possible to deduce a practical value for a shielded cell atmosphere. A drying abacus was plotted in a shielded cell of the trademark Demeter, the air temperature in the cell was 22 ° C. The curves corresponding to this test as well as others performed at 20 ° C in the environmental chamber are shown in Figure 3 attached. In this figure, the reference "Cell" represents the DEMETER cell (trademark).

The test conducted in the DEMETER cell is superimposed with the test conducted at 42% RH in the environmental chamber. This allows to identify a couple of values ​​representative of the atmosphere of a shielded cell is 20 ° C and 42% relative humidity approx. This analogy does not take into account any difference of convection between the climatic chamber and the shielded cell.

As regards total drying time at 20 ° C, considering the experimental results, it was estimated at about 7 hours at 35% humidity and 8 hours at 42% humidity.

2) Influence of the amount applied GEL Figure 4 annexed gathers curves performed for three amounts of gel deposited at 20 ° C and 42% relative humidity. This figure shows that the drying rate is little affected from 0.33 kg.m "2 and 0.42 kg.m" 2 of deposited frost. A sharper difference is visible for 0.5 kg m "2. In these conditions it therefore seems preferable to aim at relatively low application rate of about 0.3 kg m" 2.

3) EFFECT OF MOISTURE ON KINETICS

DRYING

To assess the impact of humidity, curves were plotted from the characteristic points of constant rate drying phases of the gel observed in previous tests performed at a fixed temperature. These curves are shown in Figure 5 attached. In this figure, "L" represents a linear drying at 30 ° C for 120 minutes drawn from the mean values ​​of the corresponding curve. This line has the equation y = -l, 6039x + 110.27, where x is the relative humidity in%, and y is evaporation rate (% of the initial amount of solvent). The time characteristics having been selected in the area of ​​drying at constant speed, for a given temperature, the moisture content carried in ordered vary proportionally to the speed of drying. However direct comparison from one temperature to another is not possible because the selected time characteristics are not identical for all temperatures.

This figure shows that the drying rate decreases linearly when the relative humidity increases for all temperatures, in the experimental field. The influence of humidity tends to slightly increase with decreasing temperature which is consistent.

The increase in the humidity of 10% results in a decrease in the drying speed of 16%. This shows one importance to know the drying conditions during the application of the gel in the process of the present invention.

3) INFLUENCE OF TEMPERATURE ON THE KINETIC

DRYING

For tests carried out at 42% relative humidity, a comparison of the kinetics at different temperatures is performed. The results are given in Figure 6. As before, we can evaluate that the temperature increase of 10% leads to an increase in the drying rate by about 13%.

It is therefore found the opposite effects. the increase in humidity and temperature.

drying the graphs drawn in this example make it possible to provide the necessary drying time upon application of the process of the present invention provided that the air temperature of the cladding and its relative humidity are known.

The representative field of the atmosphere of a shielded cell was estimated centered around the following values: temperature: 20 ° C and relative humidity: 40%. These values ​​were obtained by analogy by drying test in the DEMETER cell (trademark).

As regards the compatibility of drying times with a decontamination operation, the graphs show a good compatibility when the temperature is above 20 ° C and the humidity is less than about 40%. For lower temperatures or high humidities, it may be necessary to set up a convective regime in the sheath which may be achieved with a process to half speed.

example 2

In this example, the drying properties of a gel based on a mixture of silicas consisting of 8% by weight of AEROSIL 380 (trade mark) which is a fumed silica with a large specific surface area of 380 m 2 / g, and from 0.5% to 1% by weight of precipitated silica FK 310 (trademark).

The size of the residue obtained after drying in the case of Aerosil mixture 380 (trademark) and FK310 was compared to the size of the waste collected in the case of silica Aerosil 380 (trade mark) alone.

Figure 7 annexed photographs of the dry residue obtained with the mixture Aerosil 380 (trade name) and 8% and FK310 (trade name) 0.5%, referenced "A" on the one hand and the mixture Aerosil 380 (trade name) and 8% FK310 (trade mark) 1%, referenced "B", on the other hand are shown for two drying modes, one at 30 ° C and the other at temperature ambient (25 ° C).

These results show that the size of the dry residues depends little on the drying conditions which is an advantage. As regards the size of the residue, is observed in all cases it is much greater than that obtained in the case of silica Aerosil 380 alone. Here, the size of the largest residues is more than a millimeter against 600.10 "6 m in the case of Aerosil silica 380 (trademark) alone. The proportion of large residue is much more important. Meanwhile, there far fewer very small dimensions of residues may not be re-trained in the disposal of dry tailings. Without a precise quantitative analysis of the granulometric distributions can forward an order of magnitude of 2 to 3 for the increase in the average size of dry residue which is dramatic considering the small amount of silica added. the result is observed from adding 0.5% silica FK 310 (trademark). this result is very important because it shows that the present invention provides a gel having characteristics close to those of a conventional decontamination gel until it is dry in terms of contact time and comp osition. In contrast, when the gel is dry, its residues are of controlled size relatively independently of the drying characteristics due to the addition of precipitated silica. The benefits include the lack of powdery residue, sizes obtained being of the order of 0.1 to 3 mm, easy peelability of the surface residue and recovering by brushing or vacuuming.

Example 3 The viscosity modifier used in this example for the preparation of alkali gels is alumina. This is of aluminum oxide Al 2 0 3 supplied by Degussa and whose primary particle size is around 13 nm and the BET specific surface area is 100 m 2 / g.

An amount of 15 g of alumina was poured into 100 mL of water or 100 ml of a given concentration of sodium hydroxide solution. The solution was stirred using a mechanical stirrer equipped with a stirrer with three blades at a speed of 600 to 800 revolutions / min for 2 to

3 minutes. The gel obtained is homogeneous and can be sprayed with a low pressure pump marketed by FEVDI. An amount of alumina to 15 g per 100 ml of solution provides a viscosity enabling low pressure spraying (<7 bar) and ensures a long contact time with the wall since the gel does not flow on a vertical wall.

Four gels were prepared by varying the sodium hydroxide concentration between 0.5 and 5 M.

Each gel is extended to uniformly spatula on a new plate of stainless steel 304 L

(Trademark) and dimensions of 5 cm x 6 cm. The deposited mass of gel is controlled by weighing and is 500 g / m 2. The plate is then allowed to dry in an oven at 22 ° C ± 1 ° C in the presence of a significant convective air stream. The relative humidity is controlled and set to a value of 42 ± 1% considered representative moisture conditions encountered in nuclear installations ventilation ducts. then follows in time the weight loss of gel during the evaporation of solvent (water).

The mass of the two most concentrated gels soda, i.e. 2.5 and 5 M is monitored over time. The initial mass of gel deposited is 1.5 g or about 220 mg of dry alumina.

The two most concentrated gels soda, ie 2.5 and 5 million will not dry. The loss in mass of gel 2.5M reached a plateau after 5 hours and the gel mass is stabilized at about 330 mg after 24 hours. The gel further contains water and adheres to the steel plate. The mass loss of the more concentrated gel, 5 M, continues on the other hand after 24 hours and the gel still contains more water than the gel 2.5M

Both gels are therefore not suitable for the application envisaged since they do not dry quickly at a temperature between 20 ° C and 30 ° C and do not drop out of the support.

In contrast, the gel dry 0.5 M sodium hydroxide in 75 minutes and the residue is completely detached from the plate at the slightest mechanical stress. The dry gel 1 M sodium hydroxide in 2 hours and also peels off easily. It is therefore necessary to reduce the amount of soda to the water evaporates sufficiently to obtain a residue that comes off the support.

Thus a concentration of 1 to 2 mol / 1 is often preferred: it leads to a gel which dries relatively quickly, i.e. in 2 to 3 hours, and detaches very easily from the steel backing to the slightest touch.

The efficacy of gel deposited on a coated surface pump fat DELASCO (trademark), silicone grease, slightly viscous or gimbals lubricating grease called G 12, more fluid is important since 75 to 90% fat is removed from the support. The dry gel is easily detached by plates has the slightest shock and can thus be easily re-sucked. example 4

For decontamination of aluminum, silica gels AEROSIL 380 (trade name) and 8% by weight and a mixture of nitric acid and phosphoric acid were prepared. The concentration of each of the two acids is preferably below 2 mol / 1. Beyond that, the gel is not dried at a temperature of 25 ° C and a relative humidity of 40%. For a concentration of each of the two acids between 1 and M 2, the "drying time observed at a temperature of 25 ° C and a relative humidity of 40% vary between 2 and 4 hours.

A gel (3 HN0 1M / 1M H 3 P0 4) was especially prepared and tested in terms of decontamination on aluminum flanges from a pneumatic transfer network of a reprocessing plant for nuclear waste. Decontamination factor of the order of 14 (Cs 137, Eu 154) were obtained after a single pass gel (Cs 137: 1300 Bq / cm 2-110 Bq / cm 2) and the surface activity could be reduced to below 50 Bq / cm 2 with an additional pass.

example 5

For déσontaminer 1 stainless steel or Inconel (trademark), an oxidizing gel according to the invention was prepared using 3 M nitric acid and 0.l to 0.3 of Ce (IV) .

The gels quickly dry in less than 3 hours and are easily peeled off brush. The corrosion results obtained by coating 500 g / m2 on one of inconel are quite interesting since the widespread erosion effect is between 0.1 and 0. 3 microns.

Claims

1. A method of treating a surface with a treatment gel, said method comprising in this order the steps of: applying a treatment gel on the surface to be treated, said treatment gel consisting of a colloidal solution comprising :
• 5 to 25% by weight of a thickening agent inorganic or a mixture of inorganic viscosing agents based on the weight of the gel,
• 0.5 to 4 mol / 1 of an active treatment agent, and • optionally 0.05 to 1 mol / 1 of an oxidizing agent with a normal oxidation-reduction potential E 0 larger than 1.4 V in strong acid medium or of the reduced form of this oxidizing agent, - maintaining the surface treatment gel treated at a temperature and relative humidity such that the gel dries and that it has time to treat the surface before forming a dry and solid residue, and - removal of the dry residue and the solid treated surface.
2. Treatment process according to claim 1, wherein the drying temperature is between 20 and 30 ° C, and relative humidity between 20 and 70%.
3. The method of claim 1, wherein the treatment gel has a surface area greater than 100m 2 / g, a viscosity at least equal to 350 mPa.s, and a recovery time of viscosity less than 1 second.
4. Treatment process according to claim 1, wherein the gel being based on silica, silica represents from 5 to 15% by weight of the gel.
5. Treatment process according to claim 4, wherein the silica is a fumed silica, a precipitated silica or a silica mixture fumed and precipitated silica.
6. Treatment process according to claim 1, wherein the gel being based on silica mixture fumed and precipitated silica, the mixture of fumed and precipitated silicas represents from 5 to 10% by weight of the gel.
7. Treatment process according to claim 1, wherein the gel being based on silica mixture fumed and precipitated silica, the precipitated silica represents 0.5% by weight of the gel and the fumed silica represents 8% by weight of the gel.
8. Treatment process according to claim 1, wherein the gel being based on alumina, the alumina represents from 10 to 25% by weight of the gel.
9. Treatment process according to any one of claims 1 to 8, wherein the gel comprises an active treatment agent which is an inorganic acid or a mixture of inorganic acids present at a concentration of 1 to 4 moles per liter of gel.
10. A method of treatment according to claim 9, wherein the inorganic acid is selected from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or a mixture thereof.
11. Treatment process according to any one of claims 1 to 8, wherein the gel comprises an active treatment agent which is an inorganic base present in a concentration of 0.5 to 2 moles per liter of gel.
12. A method of treatment according to claim 11, wherein the inorganic base is selected from soda, potash or a mixture thereof.
13. Treatment process according to any one of claims 1 to 8, wherein the treatment gel comprises from 0.5 to 1 mol / 1 of an oxidizing agent with a normal oxidation-reduction potential E 0 greater than 1, 4 V in a strong acid medium selected from Ce (IV), Co (III) Wag (II).
14. The processing method. to claim 1, wherein the treatment gel comprises from 5 to 15% by weight of silica, from 0.5 to 2 mol / 1 of nitric acid and 0.1 to 0.5 mol, per liter of gel, Ce (N0 3) 4 or (NH 4) 2 Ce (N0 3) 6.
15. A method of treatment according to claim 1, wherein the treatment gel is applied on the surface to be treated at 100 to 2000 g of gel per m 2 of surface.
16. The method of claim 1, wherein the dry residue and the solid is removed from the treated surface by brushing and / or by suction.
17. Use of a method according to any one of claims 1 to 16 for degreasing a surface, for removing an oxide layer from a metal surface or for decontaminating a surface.
18. a plant decontamination method comprising a dedusting installation to be treated, followed by treatment of the installation by means of a method according to any one of claims 1 to 16.
19. The method of claim 18, wherein the facility is a ventilation shaft of a nuclear facility.
20. a surface treatment gel consisting of a colloidal solution comprising:
• 5 to 25% by weight of a thickening agent inorganic or a mixture of inorganic viscosing agents based on the weight of the gel, • 0.5 to 4 mol / 1 of an active treatment agent, and
• optionally 0.05 to 1 mol / 1 of an oxidizing agent with a normal oxidation-reduction potential E 0 larger than 1.4 V in a strong acid medium or of the reduced form of this oxidizing agent.
21. Gel treatment of a surface according to claim 20, consisting of a colloidal solution comprising: • 5 to 15% by weight of silica based on the weight of the gel,
• 0.5 to 4 mol / 1 of an inorganic acid or a mixture of inorganic acids, and
• optionally 0.05 to 1 mol / 1 of an oxidizing agent with a normal oxidation-reduction potential E 0 larger than 1.4 V in a strong acid medium or of the reduced form of this oxidizing agent.
22. Treatment gel according to claim
21, wherein the silica is a fumed silica, a precipitated silica or a silica mixture fumed and precipitated silica.
23. Treatment gel according to claim 21, wherein the silica is a fumed silica mixture and precipitated silica, the mixture of the fumed and precipitated silicas represents from 5 to 10% by weight of the gel.
24. Treatment gel according to claim
23, wherein the precipitated silica represents 0.5% by weight of the gel and the fumed silica represents 8% by weight of the gel.
25. Treatment gel according to claim
21 wherein the inorganic acid is selected from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or a mixture thereof.
26. Gel treatment of a surface according to claim 20, consisting of a colloidal solution comprising:
• 10 to 25% by weight alumina based on the weight of the gel, • 0.5 to 2 mol / 1 of an inorganic base or a mixture of inorganic bases, and
• optionally 0.05 to 1 mol / 1 of an oxidizing agent with a normal oxidation-reduction potential E 0 larger than 1.4 V in a strong acid medium or of the reduced form of this oxidizing agent.
27. Treatment gel according to claim 26, wherein the inorganic base is selected from soda, potash or a mixture thereof.
28. Treatment gel according to claim 21 or 26, wherein the oxidizing agent with a normal oxidation-reduction potential E 0 larger than 1.4 V in a strong acid medium is selected from Ce (IV), Co (III) or Ag (II).
EP20020760387 2001-07-17 2002-07-15 Method for treating a surface with a treating gel and treating gel Active EP1421165B1 (en)

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FR0109520A FR2827530B1 (en) 2001-07-17 2001-07-17 Process for treating a surface with a treatment gel, and treatment gel
PCT/FR2002/002509 WO2003008529A1 (en) 2001-07-17 2002-07-15 Method for treating a surface with a treating gel and treating gel

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US20060151434A1 (en) * 2005-01-07 2006-07-13 The Boc Group, Inc. Selective surface texturing through the use of random application of thixotropic etching agents
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US20040175505A1 (en) 2004-09-09 application
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FR2827530A1 (en) 2003-01-24 application
ES2271318T3 (en) 2007-04-16 grant
DE60214567D1 (en) 2006-10-19 grant
CN1592778A (en) 2005-03-09 application
JP4334339B2 (en) 2009-09-30 grant
RU2291895C2 (en) 2007-01-20 grant
CN1273578C (en) 2006-09-06 grant
JP2004535510A (en) 2004-11-25 application
RU2004104467A (en) 2005-05-10 application
EP1421165B1 (en) 2006-09-06 grant
US7718010B2 (en) 2010-05-18 grant
US20060032518A1 (en) 2006-02-16 application
US7713357B2 (en) 2010-05-11 grant

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