This description relates to a process for making metal oxide solutions for photocatalytic materials.
Photocatalytic coatings including a photocatalytically active oxide of a transition metal (MO) or (MO2) such as titanium oxide (TiO2) or zirconium oxide (ZrO2) can be used for producing self-cleaning coatings on a surface such as a glass windows.
In one general aspect, an amorphous metal peroxide solution is made by mixing hydrogen peroxide and a prepared amorphous metal hydroxide mixture to form a hydrogen peroxide and amorphous metal hydroxide mixture, and simultaneously heating and applying pressure above atmospheric pressure to the hydrogen peroxide and amorphous metal hydroxide mixture for a period of time to form the amorphous metal peroxide solution.
Implementations can include one or more of the following features. For example, the method can include preparing the amorphous metal hydroxide mixture. The amorphous metal hydroxide mixture can be prepared by mixing aqueous ammonia to a salt solution of the metal to form an amorphous metal hydroxide, and washing and separating the amorphous metal hydroxide.
The method can include adding a wetting agent to the hydrogen peroxide and amorphous metal hydroxide mixture prior to the simultaneous heating and application of pressure to form a hydrogen peroxide/amorphous metal hydroxide/wetting agent mixture.
Simultaneously heating and applying pressure above atmospheric pressure can include heating the hydrogen peroxide and amorphous metal hydroxide mixture to a temperature between about 90° C. and about 250° C.
The method can include agitating the hydrogen peroxide and amorphous metal hydroxide mixture simultaneously with heating and applying pressure to the hydrogen peroxide and amorphous metal hydroxide mixture.
The amorphous metal peroxide solution can be amorphous titanium peroxide solution, and the prepared amorphous metal hydroxide mixture can be a prepared amorphous titanium hydroxide mixture. Simultaneously heating and applying pressure above atmospheric pressure to the hydrogen peroxide and amorphous metal hydroxide mixture for a period of time can include simultaneously heating to a temperature between about 90° C. and about 250° C. and applying pressure for about 1½-2 hours to form the amorphous titanium peroxide solution.
The method can include monitoring a temperature of the hydrogen peroxide and amorphous metal hydroxide mixture while simultaneously heating and applying pressure above atmospheric pressure to the hydrogen peroxide and amorphous metal hydroxide mixture for a period of time. The method can include monitoring a pH level of the hydrogen peroxide and amorphous metal hydroxide mixture while simultaneously heating and applying pressure above atmospheric pressure to the hydrogen peroxide and amorphous metal hydroxide mixture for a period of time.
In another general aspect, a method of making amorphous metal peroxide solution includes mixing hydrogen peroxide, a prepared amorphous metal hydroxide mixture, and a wetting agent to form a hydrogen peroxide/amorphous metal hydroxide/wetting agent mixture, and treating the hydrogen peroxide/amorphous metal hydroxide/wetting agent mixture to form the amorphous metal peroxide solution.
Implementations can include one or more of the following features. For example, treating the hydrogen peroxide/amorphous metal hydroxide/wetting agent mixture can include simultaneously heating and applying pressure above atmospheric pressure to the hydrogen peroxide/amorphous metal hydroxide/wetting agent mixture for a period of time to form the amorphous metal peroxide solution.
The method can include agitating the hydrogen peroxide/amorphous metal hydroxide/wetting agent mixture simultaneously with heating and applying pressure. The method can include preparing the amorphous metal hydroxide mixture.
The amorphous metal hydroxide mixture can be prepared by mixing aqueous ammonia to a salt solution of the metal to form an amorphous metal hydroxide, and washing and separating the amorphous metal hydroxide.
The amorphous metal peroxide solution can be amorphous titanium peroxide solution, and the prepared amorphous metal hydroxide mixture can be a prepared amorphous titanium hydroxide mixture. Simultaneously heating and applying pressure above atmospheric pressure to the hydrogen peroxide/amorphous metal hydroxide/wetting agent mixture for a period of time to form the amorphous metal peroxide solution can include simultaneously heating to a temperature between about 90° C. and about 250° C. and applying pressure for about 1½-2 hours to form the amorphous titanium peroxide solution.
In another general aspect, a method of making anatase metal oxide solution includes preparing amorphous metal peroxide solution, and simultaneously heating and applying pressure above atmospheric pressure to the prepared amorphous metal peroxide solution for a period of time to form the anatase metal oxide solution.
Implementations can include one or more of the following features. For example, preparing the amorphous metal peroxide solution can be prepared by mixing hydrogen peroxide and a prepared amorphous metal hydroxide mixture to form a hydrogen peroxide and amorphous metal hydroxide mixture, and simultaneously heating and applying pressure above atmospheric pressure to the hydrogen peroxide and amorphous metal hydroxide mixture for a period of time to form the amorphous metal peroxide solution.
The method can include preparing the amorphous metal hydroxide solution.
Preparing the amorphous metal peroxide solution can include preparing an amorphous metal hydroxide mixture, mixing hydrogen peroxide and the prepared amorphous metal hydroxide to form a hydrogen peroxide and amorphous metal hydroxide mixture, and treating the hydrogen peroxide and amorphous metal hydroxide mixture to form the amorphous metal peroxide solution. Treating the hydrogen peroxide and amorphous metal hydroxide mixture can include simultaneously heating and applying pressure above atmospheric pressure to the hydrogen peroxide and amorphous metal hydroxide mixture for a period of time to form the amorphous metal peroxide solution. The method can also include adding a wetting agent to the hydrogen peroxide and amorphous metal hydroxide mixture prior to treating. Treating the hydrogen peroxide and amorphous metal hydroxide mixture can include simultaneously heating and applying pressure above atmospheric pressure to the hydrogen peroxide and amorphous metal hydroxide mixture for a period of time to form the amorphous metal peroxide solution.
The amorphous metal peroxide solution can be an amorphous titanium peroxide solution, and the anatase metal oxide solution can be anatase titanium oxide solution.
Simultaneously heating and applying pressure above atmospheric pressure to the prepared amorphous titanium peroxide solution for a period of time to form the anatase titanium oxide solution can include heating the prepared amorphous titanium peroxide solution to a temperature between about 90° C. and about 250° C. under the applied pressure until the anatase titanium oxide solution is formed.
In another general aspect, a method of applying an anatase metal oxide solution to a substrate includes making an amorphous metal peroxide solution, forming an anatase metal oxide solution from the amorphous metal peroxide solution, and applying the anatase metal oxide solution to the substrate. The amorphous metal peroxide solution is made by simultaneously heating and applying pressure above atmospheric pressure to a hydrogen peroxide and amorphous metal hydroxide mixture for a period of time to form the amorphous metal peroxide solution.
Implementations can include one or more of the following features. For example, the anatase metal oxide solution can be applied to the substrate by applying the anatase metal oxide solution as a coating to a surface of the substrate. The anatase metal oxide solution can be applied to the substrate by integrating the anatase metal oxide solution within the substrate. Integrating the anatase metal oxide solution within the substrate can include dispersing the anatase metal oxide solution within the substrate such that the anatase metal oxide solution is distributed throughout the substrate.
The time it takes to produce the amorphous metal peroxide solution is reduced because the mixture of the hydrogen peroxide and the metal hydroxide is heated simultaneously with being pressurized. The reaction does not need to be kept cool and therefore does not need to be slowly and carefully warmed up to ensure that the pH rises slowly and stably enough from the cool temperature.
Similarly, the time it takes to produce the anatase metal oxide solution is reduced because the amorphous metal peroxide solution is heated simultaneously with being pressurized. Time can be reduced to about 3 hours.
Because the wetting agent is introduced to the amorphous metal hydroxide and hydrogen peroxide mixture prior to heating and pressurizing of the mixture, the amorphous metal peroxide solution is more homogenous and therefore provides a better film or coating former. Additionally, the amorphous metal peroxide solution produced in this manner (that is, with the early introduction of the wetting agent) does not need to be intermittently shaken or agitated after formation to maintain its homogeneity. Moreover, the amorphous metal peroxide solution can be applied as a thinner coating at 12 to 18 micron droplets at ranges from 100 nm and higher film thickness regardless of the spray apparatus and the spray application parameters. Moreover, a special apparatus is not needed to apply the amorphous metal peroxide solution to obtain a coating having a thickness of at least 100 nm.
Additionally, because the time needed to complete the reactions involved in forming the solutions is reduced, the cost for producing the amorphous metal peroxide solution and the anatase metal oxide solution is also reduced.
Other features will be apparent from the description, the drawings, and the claims.
Like reference symbols in the various drawings indicate like elements.
When a metal oxide such as anatase titanium oxide TiO2 is illuminated by ultraviolet light having a wavelength below about 390 nm, electrons in the valence band are excited to the conduction band leaving behind positively-charged holes that are reactive with absorbed water vapor hydroxide ions, resulting in the formation of positively-charged hydroxyl radicals. The hydroxyl radicals are strong oxidizing radicals that can react with and strip electrons from the organic pollutants to produce simpler, non-offensive products such as CO2 and H2O. Because of these properties, anatase titanium oxide is used in photocatalytic coatings that are applied to surfaces to react with and decompose the organic pollutants deposited upon the surface from the environment under the effects of exposure to sunlight, and in particular, to ultraviolet radiation. The non-offensive products produced on the surface from the reaction with the anatase titanium oxide can re-enter the atmosphere or wash away under the effects of heat, wind, or rain.
Referring to
Examples of substrates include metals, glass, polymeric materials, textiles, building materials such as concrete and vinyl, ceramics, pigments and fillers, fiber materials, electronics, carbon, graphite, plastics, resin materials, inorganic materials, organic materials, wood, paper, waste, skin, hair, and in particular, substrates and surfaces such as surgical steel, stainless steel, medical devices, Delrin® acetal resin, Kevlar® brand fiber, polycarbonate, fiberglass, cement, and anodized aluminum.
Initially, an amorphous metal peroxide solution is prepared (step 105). The amorphous metal peroxide solution is a metal peroxide solution that is amorphous (that is, non-crystalline). The amorphous metal peroxide solution is typically not photocatalytic, but is used as a precursor to produce the photocatalytic anatase metal oxide solution, as will described later. The amorphous metal peroxide solution can be stored at room temperatures over a long time for use later, and the solution will not form the photocatalytic anatase metal oxide solution unless treated, as further discussed below. The amorphous metal peroxide solution can be applied to a surface, and then later treated to form the photocatalytic anatase metal oxide solution. The anatase metal oxide solution is prepared using the amorphous metal peroxide solution (step 110). Next, the anatase metal oxide solution can be applied (by, for example, coating, spraying, or drying) to any suitable surface as a photocatalytically-active metal oxide (step 115). Each of these steps is described in greater detail below with reference to
Referring to
Referring to
Next, the amorphous metal hydroxide mixture is washed (for example, by decantation or filtration) and separated from the chlorine ions in the mixture (step 310). The metal hydroxide mixture can be washed and separated by adding distilled water to the mixture, applying sufficient agitation to the mixture, allowing the mixture to stand, and discarding any supernatant liquid. Washing is repeated until little or no chlorine ions are detected in the supernatant liquid (for example, by using by using silver nitrate to measure levels of chlorine ions in the supernatant liquid or by using a chlorine ion probe). In some implementations, washing can be repeated until the amount of chlorine ions in the supernatant liquid is less than about 5 parts per million (ppm). In some cases, the mixture also can be subjected to centrifugal dehydration.
Additionally, water can be re-added to the mixture at this step or at later steps in suitable amounts to adjust the density of the mixture (the density being related to the amount of solid dispersed within the water). The density of the mixture can be adjusted depending on the surface or substrate to which the solution will be applied. For example, for porous or absorbent surfaces or substrates such as concrete, the density of the mixture can be relatively higher and for non-porous or non-absorbent surfaces or substrates such as glass, the density of the mixture can be relatively lower. The density of the mixture can impact the response time of the photocatalytic reaction. As the density of the mixture goes up, the thickness of the film build goes up.
Referring again to
Next, the mixture of the wetting agent, the hydrogen peroxide, and the metal hydroxide is heated simultaneously with being pressurized to a pressure that is above atmospheric pressure in combination with a suitable level of agitation for a suitable period of time until the amorphous metal peroxide solution is formed (step 220). Atmospheric pressure is the pressure at any point in the atmosphere local to the mixture due solely to the weight of the atmospheric gases above the mixture. The temperature at which the mixture is heated can depend on several factors, including the type of metal used in the mixture and constraints associated with manufacturing (for example, if the temperature needs to be lowered due to manufacturing limitations, then the time can be increased by a suitable amount). For example, a mixture of titanium hydroxide and hydrogen peroxide having a volume of about 2 liters can be heated to between about 90° C. to about 250° C. for about 1½ to 2 hours at 10 to 100 pounds per square inch (psi). For larger volumes of the mixture, for example, as used in manufacturing, the pressure can be suitably higher, for example, up to 2500 psi.
The level of agitation can be any level that provides enough agitation to disassociate the ions of the mixture and form the amorphous metal peroxide mixture. For example, the level of agitation can be between about 500 to about 10,000 rotations per minute (rpm) depending on the volume of the mixture. In some implementations, the level of agitation is between about 2500 to about 7000 rpm. During the heating and pressure application step, the mixture is monitored for temperature and pH levels to ensure that the mixture results in a completed solution in which the components (that is, the wetting agent, the hydrogen peroxide, and the metal hydroxide) are uniformly distributed throughout the mixture and to avoid forming a coagulated mixture.
After the amorphous metal peroxide solution is formed (step 220), it is allowed to cool to room temperature (step 225). The time to cool the solution can vary depending on the quantity of solution formed, the temperature at which the mixture was heated, and the metal used in the metal hydroxide. In some implementations, cooling can take between one to several hours.
The amorphous metal peroxide solution that is made (step 105) has about a 95-97% light transmissiveness. Thus, it appears clear to the human eye. Moreover, the density of the solution (that is, the amount of solid dispersed in solution) can be anywhere between 0.5 to about 2.0%, depending on the application in which the solution will be used.
Referring again to
For a density of about 1.2-1.5% anatase metal oxide, the anatase metal oxide solution can have a light transmissiveness of about 87-93% and the solution appears clear to the human eye, and the human eye would be unable to detect yellow within the solution. In some implementation, the density of the anatase metal oxide solution (that is, the amount of solid dispersed in solution) can be anywhere between 0.5 to about 2.0%, depending on the application in which the solution will be used.
Referring to
Next, the mixture of the wetting agent, the hydrogen peroxide, and the metal hydroxide is treated for a period of time until amorphous metal peroxide solution is formed (step 420). For example, one way to treat the mixture of the wetting agent, the hydrogen peroxide, and the metal hydroxide is to heat the mixture simultaneously with being pressurized to a pressure that is above atmospheric pressure in combination with a suitable level of agitation for a suitable period of time until the amorphous metal peroxide solution is formed, as described above with respect to step 220. Another way to treat the mixture is to cool the mixture to 5° C. for about 24 hours while applying agitation, as described in U.S. Pat. No. 6,429,169.
After the amorphous metal peroxide solution is formed (step 420), it is allowed to reach room temperature (step 425) by either cooling down or heating up, depending on how the mixture was treated at step 420.
Other implementations are within the scope of the following claims.
Number | Name | Date | Kind |
---|---|---|---|
4820748 | Yamamori et al. | Apr 1989 | A |
5403513 | Sato et al. | Apr 1995 | A |
5759251 | Nakamura et al. | Jun 1998 | A |
5939194 | Hashimoto et al. | Aug 1999 | A |
6013372 | Hayakawa et al. | Jan 2000 | A |
6090489 | Hayakawa et al. | Jul 2000 | A |
6099969 | Ogata | Aug 2000 | A |
6107241 | Ogata et al. | Aug 2000 | A |
6235401 | Ogata et al. | May 2001 | B1 |
6344277 | Ogata et al. | Feb 2002 | B1 |
6344278 | Ogata et al. | Feb 2002 | B1 |
6379811 | Ogata et al. | Apr 2002 | B2 |
6420437 | Mori et al. | Jul 2002 | B1 |
6429169 | Ichinose | Aug 2002 | B1 |
6524664 | Hashimoto et al. | Feb 2003 | B1 |
6565641 | Isozaki | May 2003 | B1 |
6602918 | Ichinose | Aug 2003 | B1 |
6733580 | Isozaki | May 2004 | B2 |
6736890 | Haruta et al. | May 2004 | B2 |
6770257 | Imura et al. | Aug 2004 | B1 |
6830785 | Hayakawa et al. | Dec 2004 | B1 |
6884752 | Andrews | Apr 2005 | B2 |
7090823 | Liu | Aug 2006 | B1 |
7175825 | Nakano et al. | Feb 2007 | B2 |
7205049 | Andrews | Apr 2007 | B2 |
7261942 | Andrews | Aug 2007 | B2 |
7294365 | Hayakawa et al. | Nov 2007 | B2 |
7303738 | Okusako | Dec 2007 | B2 |
7419718 | Ogata et al. | Sep 2008 | B2 |
20020016250 | Hayakawa et al. | Feb 2002 | A1 |
20050147759 | Andrews | Jul 2005 | A1 |
20050271892 | Ogata et al. | Dec 2005 | A1 |
20050279255 | Suzuki et al. | Dec 2005 | A1 |
20070248790 | Ogata | Oct 2007 | A1 |
20080035025 | Andrews | Feb 2008 | A1 |
20080166478 | Kameshima et al. | Jul 2008 | A1 |
20080241557 | Hoshi et al. | Oct 2008 | A1 |
Number | Date | Country |
---|---|---|
1253119 | May 2000 | CN |
0846494 | Jun 1998 | EP |
0854112 | Jul 1998 | EP |
1310579 | May 2003 | EP |
0816466 | May 2006 | EP |
1873218 | Jan 2008 | EP |
9071418 | Mar 1997 | JP |
9227159 | Sep 1997 | JP |
10067516 | Mar 1998 | JP |
10156999 | Jun 1998 | JP |
2000247639 | Sep 2000 | JP |
2001048538 | Jan 2001 | JP |
2007118556 | May 2007 | JP |
2005050740 | Jun 2005 | KR |
Number | Date | Country | |
---|---|---|---|
20080207440 A1 | Aug 2008 | US |