WO2010075615A1

WO2010075615A1 - Process for preparing thin or ultra-thin films and nanocomposites of metal oxide and/or metal nanoparticles for impregnating and/or coating glass, polymer, wood and metal substrates

Info

Publication number: WO2010075615A1
Application number: PCT/BR2009/000419
Authority: WO
Inventors: Sergio Mazurek Tebcherani; Sergio Da Silva Cava; Silvana Souza Netto Mandalozzo; Danielle Berger; Jarem Raul Garcia; Karen Wohnrath
Original assignee: Itajara Minérios Ltda.
Priority date: 2008-12-29
Filing date: 2009-12-23
Publication date: 2010-07-08
Also published as: BRPI0806015A2

Abstract

It seems that the title of the abstract needs to be brought into line with the title of the invention, according to PCT Rule 4.3 and to the modifications of the abstract according to PCT Rule 38.3. The title of the abstract will thus be the same as the title of the invention, as follows: process for preparing thin or ultra-thin films and nanocomposites of metal oxide and/or metal nanoparticles for impregnating and/or coating glass, polymer, wood and metal substrates.

Description

Process of Preparation of Thin or Ultra Thin Films and Nanocomposites of Metal Oxide and / or Metal Oxide Nanoparticles Impregnated and / or Deposited in Glassy, Polymeric, Wood and Metal Substrates.

The present invention comprises a method for manufacturing thin or ultra-thin films and nanocomposites of metal oxide and / or metal nanoparticles in interaction with glass substrates or

polymers or woods, metals or any other substrate which may or may cause porosity on its surface by a process of impregnation and / or deposition of metal oxides and / or metals previously formed at a temperature below the glass transition or softening point or flash point or below any temperature that will result in a change in the physical state of the material when associated with the influence of the time at which the test is performed.

It is common to find in the scientific literature studies concerning the properties of materials related to surface structure. The surface properties of materials can be modified from various deposition techniques capable of forming thin, thick or even ultra thin films. Some of these techniques are described below.

Thin films can be produced by saline deposition through the effect of temperature. Ag + ion deposition films have already been prepared on the glass surface from Ag ₂ S0 ₄ , CuS0 ₄ , Na ₂ S0 _{4 solution} in the presence of organic compounds dispersed in oil. The treatment temperature was 300 ° C, 320 ° C and 350 ° C, with time ranging from 1 to 48 h. Another way to obtain films is from the deposited by electrostatic spray, by method of sputtering method and followed by heat treatment.

The filtered cathode arc plasma and oxygen flow technique was also applied to deposit thin films of zinc oxide on glass surface and temperature of 200 ° C.

Yet another way to change the surface properties of materials is in the direct addition of dopants during the synthesis process that form new materials with new properties,

consequently also changing the surface properties.

Currently 3 types of substrates are used in the

development of thin films: 1) Metal foils, used for the manufacture of thin films for capacitors on printed circuit boards through coatings such as nickel or copper. 2) Ceramic substrates. 3) Silicon wafers for the manufacture of thin metal oxide films. It is known that a basic condition for the selection of a thin film substrate is low surface roughness.

Among the various methods for thin film manufacturing, we can mention: Sputtering, Chemical Vapor Deposition (CVD), Sol-Gel, Spray Pyrolysis, etc. All these methods have advantages and disadvantages, but in general they have difficulties such as high cost, difficulties in reproducing results, cracks.

surface and porosities.

It should also be considered that the methods described above may constitute the oxides to be obtained in the form of films only if they are mixed during the synthesis process of these materials. For the formation of films on already processed substrates the oxides are formed from precursor substances deposited on the substrates which, by treatment (usually thermal), form the oxide films to be obtained. It is noteworthy that glassy materials when subjected to high temperatures reach a "softening" state which, by definition, is known as glass transition (Tg). This glass transition is often a limiting factor for film-making and particulate material impregnation methods on the glass surface, and if it is a polymeric substrate softening can be achieved and if it is a flash point wood and metal oxidation. , etc.

The present invention comprises a method for the manufacture of thin or ultra-thin films and metal oxide nanoparticle nanocomposites in interaction with glass or polymeric substrates or woods, metals or any other substrate which may or may generate porosity on its surface. by a process of impregnation and / or deposition of metal oxide powders previously formed at a temperature below the glass transition or

softening point or flash point or even below any temperature that results in a change in the physical state of the material when associated with the influence of the time at which the test is processed.

The following drawings refer to results in exemplary form of the invention of the methodology for manufacturing thin or ultra thin films and metal oxide nanoparticle nanocomposites in interaction with glass or polymer substrates or wood, metals or any other substrate which may or may not be generated on its surface by a process of impregnation and / or deposition of metal oxides previously constituted at a temperature below the glass transition or

softening point or flash point or below any temperature that results in a change in physical state associated with the influence of the time of the test, in which:

fig. 1 is a sequence of 3,000 X magnification scanning electron microscopy ranging from pure glass substrate until the deposition of the treated nanoparticulate Sn02 film at 485 ° C.

fig. 2 represents an example of cobalt oxide deposition by EV.

fig. 3 depicts an example of iron oxide III deposition by SEM.

fig. 4 depicts an example of SEM deposition of titanium oxide.

fig. 5 depicts an example of deposition of aluminum oxide by SEM.

fig. 6 depicts an example of copper oxide deposition by SEM.

The present invention comprises a process for fabricating metal oxide thin films from films at temperatures below the glass transition temperature, or the softening temperature, or the flash point, or the change in oxidation state depending on the substrate. pressure as a function of the test time. The process consists of: (a) deposition of metal powders on the substrate surface, (b) application of high pressure cooled gas, (c) infiltration and / or deposition of powders on the substrate surface and (d) below heating temperature glass transition temperature (for glass), softening (for polymers), flash point (for wood) and oxidation (for metals) as a function of time. Following high pressure impregnation and / or deposition, the metal oxides will form a second phase, as in a composite, which depending on factors such as chemical substrate build-up, particle size and specific surface area of the metal oxide powders, gas pressure applied, type of gas, treatment time and temperature, may be in an amorphous or nanocrystalline state and may therefore form a thin film consisting or not of materials called nanocomposite. Figure 1 shows an example of thin film of metal oxides impregnated and / or deposited by high limit pressure (Pi.) On substrate. In Figure 1 it can be seen that even at the pressure P | _, at point (1) the substrate does not undergo any treatment (temperature T ₀ = 0 and time t ₀ = 0), consequently the metal oxide and / or metal is not deposited.

With application of limit pressure or greater than PL, in

heat treatment at a temperature T and a time it can be seen that impregnation and / or deposition of the metal oxide and / or metal with the substrate begins to occur leading to point (2) of Figure 1.

When the limit pressure is kept constant, film deposition and / or impregnation can be improved by raising the temperature from ΤΊ to T ₂ or increasing the time from ti to t ₂ or raising the temperature and time to T ₂ and t _2. respectively. However, by keeping the temperature in Ti and the time constant in Ti, but by raising the pressure above PL it is also possible to achieve a film indicated by stage (3) of Figure 1.

Similarly, still in figure 1, stage 3 can be reached if: the limit pressure is kept constant and the temperature of T ₂ is raised to T3 or, if the time is increased from t ₂ to t. ₃ or raise both to T3 and respectively. In this same example, the same result is also achieved if the temperature at T ₂ and the time at t ₂ remain constant, but if the applied pressure is greater than the pressure exerted at stage (2).

Thus, it is proved that by applying a very high pressure, and a temperature T _n (where n is greater than zero) which varies to, temperature below the glass transition temperature when the substrate is glass, temperature below temperature of

softening when substrate is polymer, temperature below flash point when substrate is wood and temperature below oxidation temperature for metals and a time t _m (where m is a value greater than zero) one can have a different methodology for obtaining thin or ultra thin films and nanocomposites of metal oxide and / or metal nanoparticles in interaction with glass or polymer substrates or woods, metals or any other substrate presenting or porosity may be generated on its surface by a process of impregnation and / or deposition of the high pressure as a function of time.

In turn, the figures from figure 2 to figure 6 demonstrate the possibility of applying different substrate oxides when applying a pressure equal to or greater than P (- a temperature Ti or above and a time at least be you.

Still referring to the figures already mentioned and, according to the proposal of this process of preparing films on substrates, it is possible to verify the possibility of impregnating and / or depositing cobalt oxide (figure 2), iron oxide III (figure 3 ), titanium oxide (figure 4), aluminum oxide (figure 5), copper oxide (figure 6) or any other type of metal and / or metal oxide on glass, polymer, wood or metal substrates, provided the pressure, temperature and time conditions proposed in this inventive process are respected.

Claims

1. PROCESS FOR PREPARING FINE OR ULTRA MOVIES

FINE AND NANOCOMPOSITES OF METALLIC AND / OR METAL OXIDE NANOParticles, and / or deposited in GLASS, POLYMERIC, WOOD, METAL SUBSTRATES

AND OTHER comprising the steps of: selection of metal oxide and / or metal powders; deposition of metal oxide and / or metal powders on the surface of the glass, polymer, wood, metal substrate or composition thereof; infiltration and / or deposition of metal oxide and / or metal powders on the substrate by the action of high gas pressure and temperature below: glass transition temperature for glass, softening temperature for polymers, flash point for wood. oxidation state change temperature for metals at a given time forming a thin layer of metal oxides and / or metal infiltrated and / or deposited on the substrate.

2. PROCESS FOR PREPARING FINE OR ULTRA MOVIES

FINES AND NANOCOMPOSITS OF IMPREGNED METAL AND / OR METAL OXIDE NANOParticles, AND / OR DEPOSITED IN GLASS, POLYMER, WOOD, METAL AND OTHER SUBSTRATES, as claimed, where the selected metal oxide and / or metal oxide powders are selected from one another. from the definition of pure ceramic oxides or mixtures thereof or from the definition of metal bonding to metals comprising all natural elements listed in the periodic table even in different proportions.

3. PROCESS FOR PREPARING FINE OR ULTRA MOVIES

FINES AND NANOCOMPOSITS OF IMPREGNED METAL AND / OR METAL OXIDE NANOParticles, AND / OR DEPOSITED IN GLASS, POLYMER, WOOD, METAL AND OTHER SUBSTRATES, as claimed in claim 1, where the substrate may be of any chemical composition provided that it is classified as: glass, polymer, wood, metal or, pure or mixtures of different proportions.

4. PROCESS FOR PREPARING FINE OR ULTRA FILMS AND OXIDE NANOPARTICULATE NANOCOMPOSITS

METALS AND / OR METALS IMPREGNED AND / OR DEPOSITED IN GLASS, POLYMERIC, WOOD, METAL AND OTHERS SUBSTRATES, according to claim 1, where the pressure applied to the metal oxide and / or metal powders against the substrate surface is 1-200 bar. or more preferably between 5-50 bar, or more preferably between 15-25 bar.

5. PROCESS FOR PREPARING FINE OR ULTRA MOVIES

FINES AND NANOCOMPOSITS OF METAL AND / OR METAL OXIDE NANOPARTICULES IMPREGNED AND / OR DEPOSITED IN GLASS, POLYMERIC, WOOD, METAL SUBSTRATES

AND OTHER where the temperature is controlled at a temperature above room temperature provided that deposition and / or impregnation of metal and / or metal oxides is required and below the temperature of: glass transition to glass substrates,

softening for polymer substrates, flash point for wood substrates and oxidation state change temperature and, if the composition thereof, the lowest temperature is respected.

6. PROCESS FOR PREPARING FINE OR ULTRA FILMS AND OXIDE NANOPARTICULATE NANOCOMPOSITS

METALS AND / OR METALS IMPREGNED AND / OR DEPOSITED IN GLASS, POLYMERIC, WOOD, METAL AND OTHER SUBSTRATES, where high pressure gas is selected from a group consisting of atmospheric air, neutral, reducing or oxidizing atmospheres and their combinations in any proportion .

7. PROCESS FOR PREPARING FINE OR ULTRA MOVIES

FINES AND NANOCOMPOSITS OF METAL AND / OR METAL OXIDE NANOParticles, AND / OR DEPOSITED IN GLASS, POLYMERIC, WOOD, METAL AND OTHER SUBSTRATES, where the thickness of the film obtained depends on the particle size and / or metal oxide particle size. substrate, applied pressure and temperature and heat treatment time.

8. PROCESS FOR PREPARING FINE OR ULTRA FILMS IS NANOOCOMPOSITES OF OXID NANOParticles

METALS AND / OR METALS IMPREGNED AND / OR DEPOSITED IN GLASS, POLYMERIC, WOOD, METAL AND OTHER SUBSTRATES, where the originating film is made from metallic oxides and / or metals deposited together with the substrate.