CZ301149B6 - Detoxication and decontamination suspension for moisture-proof surfaces - Google Patents

Abstract

In the present invention, there is disclosed a detoxication and decontamination suspension for moisture-proof surfaces prepared based on nanocrystalline oxides or oxide-hydroxide of metals particularly Ti, Al or Fe, and mixed compounds thereof, especially Ti/Al, Ti/Fe or Ti/Zn, wherein the invention is characterized in that at least one oxide or metal oxide-hydroxide or a mixed compound thereof is dispersed in one non-polar solvent or a mixture of non-polar solvents being selected from the group consisting of alkanes or cycloalkanes containing 6 to 10 carbon atoms or 12 to 16 carbon atoms and/or aromatic hydrocarbons containing 7 to 8 carbon atoms and/or aliphatic or cycloaliphatic ethers and/or hydrofluorinated ethers, whereas the suspension contains per each 100 grams of a powder nanocrystalline oxide or oxide-hydroxide 100 to 600 ml of a non-polar solvent or a mixture of such solvents.

Description

Detoxification and decontamination suspensions for non-absorbent surfaces of materials

Technical field

The present invention is in the field of means for detoxifying and decontaminating non-absorbent, corrosion-sensitive surfaces and materials of military, transport, industrial and agricultural machinery or technical equipment, interiors and technical components of building objects, such as optical and electronic equipment components or konio laminated with liquid militarily important or industrial highly toxic substances.

The invention then relates to a new composition of a detoxification and decontamination suspension based on metal oxides or oxides and oxides or oxides of their mixed compounds.

BACKGROUND OF THE INVENTION

At present, decontamination mixtures are used in special units of the army, fire protection and the whole integrated rescue system, which, although they show satisfactory detoxification efficiency, are nevertheless unbearable material aggressive to corrosive sensitive surfaces and components of sensitive technology. damage. As a result, it is unacceptable to reduce the basic technical and performance parameters of sensitive technology and damage their surface. There is no mixture that meets both the requirements for negligible material aggression and the requirements for sufficient efficiency and speed of detoxification of the sensitive technique.

Most of the existing standard liquid mixtures, except for dispersion mixtures such as foams, emulsions and microemulsions, and mixtures with targeted rheotropic properties, do not stick to vertical smooth surfaces for a sufficient amount of time after spraying but rather run down relatively quickly, reducing the likelihood of achieving the required decontamination effect. .

It was found that nanocrystalline oxides of some metals, such as Mg, Ca, Al, Zn, Ti and Fe, characterized by high dispersity, wherein the specific surface area can reach values higher than 200 nr.g ^first Although non-aggressive in material terms, they exhibit destructive reactivity towards militarily important toxic substances, such as both organophosphorus and blistering substances. Magnesium, calcium, aluminum, zinc, iron, and especially titanium dioxide in crystalline form of anatase, or oxides of the mentioned metals modified with various additives, for example polyoxometalalates, have the ability to effectively break these substances into human non-toxic products. These findings are reported, for example, in Wagner, GW et al: Journal Phys. Chem. B, 1999, 103, pp. 3225-3228; Wagner, GW et al: Journal of Molecular Catalysis and Chemical 144 (1999), pp. 419-424; Wagner, GW et al: Journal Phys. Chem. B, 2000, 104, pp. 5118-5123;

Koper, O. et al; Metal Oxide Nano Particles as Countermeasures against Chemical and Biological Threats. In: Proceedings of the Joint Chemical and Biological Decontamination Conference, Salt Lake City, May 2000; Wagner, G.W. et al: JournalAmer. Chem. Soc., 2001, 123, pp. 1636-1644. It is verified that the reactions of these substances take place predominantly only on the surface of the pulverulent oxides, and these behave as stoichiometric agents, i.e. they are gradually consumed in the reaction. The surface of the powdered nanocrystalline reagent itself is not uniform in reactivity. Grain edges and dislocations on their surface show higher activity. The total decomposition reaction is called destructive sorption. If contaminated real surfaces are detoxified by a simple deposit of a layer of dry nanocrystalline powder oxides on a surface on which the liquid phase of the toxic substance is present, then the rate of surface detoxification depends not only on the reactivity of the powder reagent but and the vapor pressure and evaporation rate of the toxic flux from the contaminated material to the oxide layer. Then, when detoxifying a toxic substance having a low vapor pressure, its rate of destruction and thus the observed efficacy of the agent is also determined by its rate of evaporation. Therefore, a sufficient degree of detoxification of low volatile substances, e.g. VX, chemically expressed as S- [2- (Diisopropylamino) ethyl] O-ethylmethylphosphonothioate, can be achieved for up to several hours.

The application of nanocrystalline metal oxides has also been reported, consisting in dispersing a powdering agent into a cream intended to form a protective preventive coating on human skin, see, for example, Koper, O .; Lucas, E; Klabunde, K. J .: Journal Appl. Toxicoi, 19, S59-70 (1999).

WO 03/084871 A2 relates to the preparation of stable dispersions of spherical nanocrystalline metal oxides in non-aqueous media. According to the present invention, such dispersions may find use as a component in transparent coatings on surfaces which impart some unique properties, such as abrasion resistance, radiation absorbency and catalytic function. According to the file, dispersions can also be used as a component of abrasive or polishing fluids, heat transfer fluids, as a crystalline additive, electrorheid logical fluid, etc. However, the application of dispersions for detoxifying militarily important toxic substances is not mentioned in the file.

Similarly, this application is not disclosed in US 2004/0022973 A1, where a method for preparing a plurality of monodisperse nanoparticles is solved by a multistep process.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a means which, using the latest developments in nanotechnology, removes the drawbacks of existing detoxification and decontamination mixtures.

SUMMARY OF THE INVENTION

This object is achieved by the invention, which is a detoxification and decontamination suspension for non-absorbent surfaces of materials formed from nanocrystalline metal oxides or oxide-hydroxides, in particular Ti, Al or Fe, and mixtures thereof, in particular Ti / Al, Ti / Fe or Ti / Zn, characterized in that at least one metal oxide or oxide-hydroxide or a mixed compound thereof is dispersed in one or a mixture of non-polar solvents selected from the group consisting of alkanes or cycloalkanes containing 6 to 10 carbon atoms or 12 to 16 carbon atoms and / or aromatic hydrocarbons having 7 to 8 carbon atoms and / or aliphatic or cycloaliphatic ethers and / or hydrogenfluorinated ethers, each containing 100 to 600 ml of a non-polar solvent or a mixture thereof for every 100 grams of nanocrystalline oxide or hydroxide hydroxide powder.

In a preferred embodiment, aliphatic C cycloaliphatic ethers of nonpolar solvents selected from the group defined by the formula C _n H _{(2n +} i) -OC _n H (2n + i), where index "is equal to 2-6, and the hydrofluoroalkane ethers nonpolar solvents are selected from groups defined by the general formula C _n H <2 _{n +} F9 irCM2 _4, wherein the index "is equal to 1 or 2 respectively.

Finally, it is preferred that the slurry comprises a mixture of non-polar solvents comprising 5 to 85 parts by volume of alkanes or cycloalkanes having a carbon number of 6 to 10, 5 to 50 parts by volume of aromatic hydrocarbons, further 5 to 20 parts by volume of alkanes or cycloalkanes of carbon numbers 12 to 16, further 0.1 to 20 parts by volume of aliphatic or cycloaliphatic ethers and 10 to 85 parts by volume of hydrogenfluorinated ethers.

The advantage of the present slurry is that it is prepared in the form of a thick slurry that very well wets all conventional non-absorbent surfaces and adheres to vertical surfaces, and can be easily applied by spraying with high pressure spraying techniques. The suspension is sufficiently stable and thus provides the prerequisite for the decontaminated surface to be effectively coated throughout the treatment with a layer of sufficient thickness, preferably about 1 mm, to achieve the desired degree of detoxification. The slurry layer, when formed on contaminated surfaces of sufficient thickness, acts as a chemically active barrier protecting the environment from vapors of toxic substances that would otherwise spread freely from the surface of the contaminated material to the environment. The mixture of non-polar hydrocarbons dissolves the toxic substance well and can help it

Q1 301149 B6 if the substance has already penetrated the structure.

The solvents used gradually evaporate from the surface of the deposited layer, whereby their evaporation causes transport of the dissolved toxic substance in the layer from the bottom along the microcrystallites of the powdered agent upwards to the surface, facilitating contact of the agent with the agent at the active sites of the microcrystallites. Furthermore, the non-polar solvents used favorably stimulate the chemical reaction, being inert to the vast majority of corrosion-sensitive metal and plastic materials, the hydrogenfluorinated ethers being environmentally acceptable and imparting a reduced flammability to solvent mixtures. The selected organic solvents further improve the solubility of the droplets of lipophilic toxic substances, including their so-called "thickened" recipes, present on the contaminated surfaces.

DETAILED DESCRIPTION OF THE INVENTION

The invention is illustrated in greater detail by the following formulation compositions of detoxification and decontamination suspension formulations:

Example 1

To prepare about 1 liter of suspension, use:

- 285 g of nanodisperse titanium dioxide (anatase),

- 600 ml nonane,

-130 ml light paraffin oil (Paraffin Liquidum, CAS 8042-47-5),

130 ml of methoxy-nonafluorobutyl ether.

Example 2

To prepare about 1 liter of suspension, use:

- 285 g of nanodisperse titanium dioxide (anatase),

- 515 ml nonane,

- 170 ml light paraffin oil (Paraffin Liquidum, CAS 8042-47-5),

- 170 ml of ethoxy-nonafluorobutyl ether.

The suspension is characterized by a reduced flammability and a longer solvent evaporation time, ie active action.

Example 3

For preparing about 1 liter of suspension:

- 285 g of nanodisperse titanium dioxide (anatase),

- 130 ml light paraffin oil (Paraffin Liquidum, CAS 8042-47-5),

- 340 ml of methoxy-nonafluorobutyl ether,

- 385 ml cyclohexane.

A suspension is characterized by a greater ability to dissolve toxic substances, including thickened recipes, and to extract them more effectively from the structure of contaminated materials.

Example 4

To prepare about 1 liter of suspension, use:

- 330 g of nanodisperse alumina, -3300 ml of nonane,

- 190 ml of ethoxy-nonafluorobutyl ether,

- 150 ml of diisopropyl ether,

-190 ml cyclohexane.

Example 5

To prepare about 1 liter of suspension, use:

- 285 g of nanodisperse iron oxide hydroxide (ferrihydrite),

- 600 ml nonane,

- 170 ml light paraffin oil (Paraffin Liquidum, CAS 8042 47-5),

- 85 ml of ethoxy-nonafluorobutyl ether.

Example 6

To prepare about 1 liter of suspension, use:

- 285 g of mixed nanodisperse titanium dioxide and zinc oxide hydroxide,

- 600 ml nonane,

- 170 ml light paraffin oil (Paraffin Liquidum, CAS 8042-47 5),

- 85 ml of ethoxy-nonafluorobutyl ether.

Example 7

For the preparation of about 1 liter of suspension is used;

- 220 g of mixed nanodisperse titanium dioxide and alumina-iron oxide hydroxide,

- 620 ml nonane,

- 180 ml light paraffin oil (Paraffin Liquidum, CAS 8042-47-5),

- 90 ml of methoxy-nonafluorobutyl ether.

Example 8

To prepare about 1 liter of suspension, use:

- 300 g of mixed nanodisperse titanium dioxide and zinc oxide hydroxide,

- 300 ml xylene,

- 150 ml light paraffin oil (Paraffin Liquidum, CAS 8042-47-5),

-100 ml of ethoxy-nonafluorobutyl ether.

Industrial applicability

The detoxifying and decontamination suspensions of the present invention can be prepared and applied under field and other operating conditions for the disposal of virtually all types of potentially useful highly toxic substances from non-absorbent surfaces of a sensitive technique, and exhibiting good decontamination efficiency even at low temperatures where some standard aqueous decontamination mixture is conditioned by heating. The suspension shows a high decontamination activity against all hazardous substances when (3,3-Dimethylbutan-2-yl) methylphosphonofluoridate, S- [2- (Diisopropylamino) ethyl] -O-ethyl20-methylphosphonothioate and Bis (2) are used as test toxicants. -chloroethyl) sulfide.

Claims (3)

PATENT CLAIMS 1. Detoxification and decontamination suspension for non-absorbent surfaces of materials formed from nanocrystalline metal oxides or metal oxide-hydroxides, in particular Ti, Al or Fe, and mixtures thereof, in particular Ti / Al, Ti / Fe or Ti / Zn, that at least 30 one metal oxide or oxide-hydroxide or a mixed compound thereof is dispersed in one or a mixture of non-polar solvents selected from the group consisting of alkanes or cycloalkanes containing 6 to 10 carbon atoms or 12 to 16 carbon atoms and / or aromatic hydrocarbons containing 7 to 8 carbon atoms; / or aliphatic or cycloaliphatic ethers and / or hydrogenfluorinated ethers, containing for each 100 grams of powdered nanocrystalline oxide or hydroxide-hydroxide 35 suspension of 100 to 600 ml of a non-polar solvent or a mixture thereof. Detoxification and decontamination suspension according to claim 1, characterized in that the aliphatic or cycloaliphatic ethers of the non-polar solvents are selected from the group defined by the formula C _n H (2 _n + i) -OC _n H (2 _n + i), wherein the index n is 2 to 6. Detoxification and decontamination suspension according to claim 1, characterized in that the hydrogenfluorinated ethers of the non-polar solvents are selected from the group defined by the general formula C _n H (2n + 1) -O-C ₄ F ₉ , wherein the index n is 1 or 2. Detoxification and decontamination suspension according to one of Claims 1 to 3, characterized in that it contains a mixture of non-polar solvents comprising 5 to 85 parts by volume of alkanes or cycloalkanes having a carbon number of 6 to 10, furthermore 5 to 50 parts by volume of aromatic hydrocarbons. 5 to 20 parts by volume of alkanes or cycloalkanes having a carbon number of 12 to 16, further 0.1 to 20 parts by volume of aliphatic or cycloaliphatic ethers and 10 to 85 parts by volume 50 parts hydrogenfluorinated ethers.