US20200407232A1
2020-12-31
16/457,983
2019-06-29
US 10,894,720 B1
2021-01-19
-
-
Anthony J Zimmer | Ricardo D Morales
Dale Jensen, PLC | Dale Jensen
2039-06-29
Certain exemplary embodiments can provide a reactive nano silicate, which can comprise a silica/acid composite comprising reactive functional groups activated by an intramolecular disturber. The reactive functional groups can comprise at least one of —SiH, —SiOH, silazane, durazane, polysilazane, and spiro silazane. The intramolecular disturber can comprise at least one of Fe2O3, Xe2O, SnO2, Al2O3, SiO2, TiO2, or a rare earth element oxide.
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B82Y30/00 » CPC further
Nanotechnology for materials or surface science, e.g. nanocomposites
C01P2002/01 » CPC further
Crystal-structural characteristics depicted by a TEM-image
C01P2002/88 » CPC further
Crystal-structural characteristics defined by measured data other than those specified in group by thermal analysis data, e.g. TGA, DTA, DSC
C01P2004/64 » CPC further
Particle morphology; Particles characterised by their size Nanometer sized, i.e. from 1-100 nanometer
C01P2006/32 » CPC further
Physical properties of inorganic compounds Thermal properties
C01P2006/90 » CPC further
Physical properties of inorganic compounds Other properties not specified above
C01B33/20 » CPC main
Silicon; Compounds thereof Silicates
FIG. 001, FIG. 002, FIG. 003, FIG. 004, FIG. 005, FIG. 007, FIG. 008, and FIG. 009 are executed in color. A wide variety of potential practical and useful embodiments will be more readily understood through the following detailed description of certain exemplary embodiments, with reference to the accompanying exemplary drawings in which:
FIG. 001 is a transmission electron microscopy (“TEM”) image of an exemplary silica/acid composite in a house-painting product;
FIG. 002 is a schematic diagram of an exemplary reactive nano silicate (“RNS”) process;
FIG. 003 is a photograph of a water drop on a dry surface coated with RNS;
FIG. 004 is a graph of thermal gravimetric analysis (“TGA”) data of an exemplary silica/acid composite (“SAC”) and RNS;
FIG. 005 is a Fourier-transform infrared spectroscopy (“FtIR”) chart of exemplary SAC and RNS substances;
FIG. 006A illustrates a TEM image of an exemplary SAC (shown on left) and an exemplary RNS (shown on right) (the image scale is 200 nm);
FIG. 006B illustrates a TEM image of an exemplary SAC (shown on left) and an exemplary RNS (shown on right) (the image scale is 100 nm);
FIG. 006C illustrates a TEM image of an exemplary SAC (shown on left) and an exemplary RNS (shown on right) (the image scale is 50 nm);
FIG. 006D illustrates a TEM image of an exemplary SAC (shown on left) and an exemplary RNS (shown on right) (the image scale is 20 nm);
FIG. 007 is a graph of TGA data of styrene-butadiene rubber (“SBR”) doped with a graphene hybrid composite (“GHC”) in the presence of an exemplary RNS;
FIG. 008 is a graph of TGA data of SBR doped with GHC without RNS;
FIG. 009 is a graph of TGA data of Natural Rubber (“NR”) doped with GHC in the presence of an exemplary RNS; and
FIG. 010 is a schematic representation of a band gap model of electron transfer between SAC and disturber molecules.
Certain exemplary embodiments can provide a reactive nano silicate, which can comprise a silica/acid composite comprising reactive functional groups activated by an intramolecular disturber. The reactive functional groups can comprise at least one of —SiH, —SiOH, silazane, durazane, polysilazane, and spiro silazane. The intramolecular disturber can comprise at least one of Fe2O3, Xe2O, SnO2, Al2O3, SiO2, TiO2, or a rare earth element oxide.
Silica particles (chemically “SiO2”) are very inert and can be utilized as reinforcement filler for rubber.
However, poor compatibility of silica with rubber can result in a use of further energy and chemicals, such as surfactants, to embed silica into a rubber substance.
U.S. Patent Publication 20180099905 (the “'905 Publication”) disclosed a composite formed from liquid glass with specific carboxylic acid. In the '905 Publication, liquid glass is extracted from paddy husk, which husk originated in Vietnam. The product can be called a silica/acid composite (“SAC”), which exhibits a primary particle size in the range of approximately 5 nm. These primary particles can stick to each other to form a translucent white gel.
In an attempt to find out if the SAC gel can be used as a nano additive to improve material durability, SAC was mixed with naked (i.e., no polymeric binder) water based house painting to test out water proofing properties. The conventional house paint comprising an emulsion polymer prevented at least 70% water penetration. The adding of 30% of the SAC gel into the house paint containing no emulsion polymer did not provide any prevention of water penetration through painting layer.
FIG. 001 is a TEM image of an exemplary silica/acid composite in a house-painting product as described in the '905 Publication. FIG. 001 illustrates a colorant 1100 and a SAC 1200. One can recognize that upon drying under atmospheric conditions for approximately 72 hours, the SAC accumulated into agglomerates on the surface of colorant 1100 but did not fully cover colorant 1100. This result showed that SAC was not capable of fully shielding colorant 1100 of the house-painting product from water attack.
In another exemplary of the embodiment, SAC was added onto rubber latex. The mixture was uniform due to relatively good compatibility between SAC and rubber latex. However, upon being dried, the rubber comprising SAC did not show any significant improvement in physical properties.
Based upon these tests, it was concluded that SAC is relatively inert and non-reactive. The SAC showed smaller particle sizes than other gels, but was not found to be robust enough to cause any significant enhancement in material durability.
In an attempt to change the nature of SAC, we successfully incorporated an SAC disturber into the network, which can convert the non-reactive SAC into reactive species named as reactive nano silicate (RNS), which is more interactive with other materials. The SAC disturbing molecule can be in the SAC family, but not exactly the same physical structure. Examples of the SAC disturber are metal oxides such as, but not limited to, Fe2O3, TiO2, Xe2O, SnO2, Al2O3, SiO2, TiO2, V2O5, In2O3, rare earth oxide such as La2O3, lanthanium oxide, cerium oxide, neodymium oxide, samarium oxide, and the like.
RNS is suspected to carry various reactive functional groups provided from different silicate sources, for example, but not limited to:
FIG. 002 is a schematic diagram of an exemplary RNS process. One can see that in order to form a RNS, there is a need of a disturber molecule other than SAC.
The RNS has been shown to be self-reactive and capable to form a rigid solid film upon drying. Accordingly, RNS has film-forming properties. FIG. 003 is a photograph of a water drop on a dry surface coated with RNS. The photograph shows that a dried film of RNS repels water.
At this point in time, the exact chemical structure of RNS is still unknown. The following experiments verified that RNS does exist.
FIG. 004 is a graph of thermal gravimetric analysis data of an exemplary silica/acid composite SAC and RNS. One can recognize that SAC is substantially thermally decomposed at approximately 150° C. while the RNS continued to survive beyond approximately 800° C., which suggests that SAC individual particles connect to each other into RNS due to the presence of the disturber, which in this embodiment was fumed silica.
FIG. 005 is an FtIR chart of exemplary SAC and RNS substances. FIG. 005 is an FtIR chart of an exemplary SAC (in red) and an exemplary RNS (in black). These charts are overlaid to show that the SAC and RNS are different species.
FIG. 006A illustrates a TEM image of an exemplary SAC (shown on left) and an exemplary RNS (shown on right) (the image scale is 200 nm). In another exemplary of the embodiment, FIGS. 006A, 006B, 006C, and 006D respectively exhibits TEM images of SAC (left) and of RNS (right) taken in various scales. One can recognize that SAC appears as individual particle while RNS shows a particle connected into cloudy membrane. Thus, this is evidence that SAC and RNS are different species.
Now, it can be suggested that the stranger molecule added on the solution of SAC, somehow, had successfully disturbed the structure of SAC and converted the non-reactive nature of SAC into reactive species, which is RNS. RNS can have a strong intramolecular interaction to form a film.
In another exemplary of the embodiment, GHC (as disclosed in U.S. Pat. No. 9,460,827) was added with different levels into KRL341 SBR (obtained from Kumho, a company of South Korea) containing RNS. KRL341 SBR is a commercially available SBR, which is a synthetic rubber as opposed to a natural rubber. The mixture was baked at approximately 85° C. for approximately 72 hours then exposed to TGA test. The data is illustrated in FIG. 007. FIG. 007 is a graph of TGA data of SBR doped with GHC in the presence of an exemplary RNS. One can recognize the heat resistance of SBR increased with increased concentration of GHC. Another exemplary of the embodiment that GHC alone added into SBR showed no apparent reinforcement as seen in FIG. 008. FIG. 008 is a graph of TGA data of SBR doped with GHC without RNS.
In another exemplary of the embodiment, the above experiment was repeated except that Natural Rubber (“NR”) was used instead of SBR. FIG. 009 is a graph of TGA data of Natural Rubber (“NR”) doped with GHC in the presence of an exemplary RNS. A similar reinforcement effect was observed with NR doped with GHC in the presence of RNS.
It is suggested from this result that RNS is reactive; RNS can react with both rubber and GHC and enable chemical bonding of GHC into rubber. Without RNS, GHC is substantially inert relative to rubber such as SBR and natural rubber. The chemical bonding of GHC with rubber can cause reinforcement of rubber with GHC.
It should be recognized from the above results that the reinforcement effect of rubber with GHC is due to crosslinking of rubber polymer chain via a GHC/RNS bridge. The crosslinking of rubber chain in this case is similar to the traditional sulfur vulcanization. However, the crosslinking due to GHC/RNS occurs at as low a temperature as approximately 85° C. This is actually a low temperature cure system.
Certain exemplary embodiments can provide a reactive nano silicate, which can comprise a silica/acid composite comprising reactive functional groups activated by an intramolecular disturber. The reactive functional groups can comprise at least one of —SiH, —SiOH, silazane, durazane, polysilazane, and spiro silazane. The intramolecular disturber can comprise at least one of Fe2O3, Xe2O, SnO2, Al2O3, SiO2, TiO2, or a rare earth element oxide.
The mechanism causing increased reactivity of SAC by disturber molecule is not clear at this point in time. However, specific disturber molecules somehow become molecularly coupled to SAC and successfully transfer electrons from SAC into disturber molecules causing electron starving of SAC and increased SAC reactivity as illustrated in FIG. 010. FIG. 010 is a schematic representation of a band gap model of electron transfer between SAC and disturber molecules.
According to this model, SAC should be more electrically conductive than disturber. The thermal electron from conduction band of SAC can be transferred into conduction band of disturber. Thus, disturber is relatively more electron acceptor than SAC. The disturber can be found in a group of oxides such as, but not limited to, Fe2O3, Xe2O, SnO2, Al2O3, SiO2, TiO2, or a rare earth element oxide.
The reactive nano silicate can exhibit intramolecular interaction caused by the reactive functional groups. The reactive nano silicate can exhibit:
The reactive nano silicate can be reactive with:
The reactive nano silicate can be used as a precursor to:
When the following terms are used substantively herein, the accompanying definitions apply. These terms and definitions are presented without prejudice, and, consistent with the application, the right to redefine these terms during the prosecution of this application or any application claiming priority hereto is reserved. For the purpose of interpreting a claim of any patent that claims priority hereto, each definition (or redefined term if an original definition was amended during the prosecution of that patent), functions as a clear and unambiguous disavowal of the subject matter outside of that definition.
Still other substantially and specifically practical and useful embodiments will become readily apparent to those skilled in this art from reading the above-recited and/or herein-included detailed description and/or drawings of certain exemplary embodiments. It should be understood that numerous variations, modifications, and additional embodiments are possible, and accordingly, all such variations, modifications, and embodiments are to be regarded as being within the scope of this application.
Thus, regardless of the content of any portion (e.g., title, field, background, summary, description, abstract, drawing figure, etc.) of this application, unless clearly specified to the contrary, such as via explicit definition, assertion, or argument, with respect to any claim, whether of this application and/or any claim of any application claiming priority hereto, and whether originally presented or otherwise:
Moreover, when any number or range is described herein, unless clearly stated otherwise, that number or range is approximate. When any range is described herein, unless clearly stated otherwise, that range includes all values therein and all subranges therein. For example, if a range of 1 to 10 is described, that range includes all values therebetween, such as for example, 1.1, 2.5, 3.335, 5, 6.179, 8.9999, etc., and includes all subranges therebetween, such as for example, 1 to 3.65, 2.8 to 8.14, 1.93 to 9, etc.
When any claim element is followed by a drawing element number, that drawing element number is exemplary and non-limiting on claim scope. No claim of this application is intended to invoke paragraph six of 35 USC 112 unless the precise phrase “means for” is followed by a gerund.
Any information in any material (e.g., a United States patent, United States patent application, book, article, etc.) that has been incorporated by reference herein, is only incorporated by reference to the extent that no conflict exists between such information and the other statements and drawings set forth herein. In the event of such conflict, including a conflict that would render invalid any claim herein or seeking priority hereto, then any such conflicting information in such material is specifically not incorporated by reference herein.
Accordingly, every portion (e.g., title, field, background, summary, description, abstract, drawing figure, etc.) of this application, other than the claims themselves, is to be regarded as illustrative in nature, and not as restrictive, and the scope of subject matter protected by any patent that issues based on this application is defined only by the claims of that patent.
1. A reactive nano silicate, comprising:
a silica/acid composite comprising reactive functional groups activated by an intramolecular disturber, wherein:
the reactive functional groups comprise at least one of —SiH, —SiOH, silazane, durazane, polysilazane, spiro silazane;
the intramolecular disturber is an oxide that comprises at least one of Fe2O3, Xe2O, SnO2, Al2O3, SiO2, TiO2, or rare earth element oxide.
2. The reactive nano silicate of claim 1, wherein:
the reactive nano silicate exhibits intramolecular interaction caused by the reactive functional groups.
3. The reactive nano silicate of claim 1, wherein:
the reactive nano silicate exhibits film forming properties.
4. The reactive nano silicate of claim 1, wherein:
the reactive nano silicate exhibits water proofing properties.
5. The reactive nano silicate of claim 1, wherein:
the reactive nano silicate exhibits flame retardant properties.
6. The reactive nano silicate of claim 1, wherein:
the reactive nano silicate exhibits heat resistant properties.
7. The reactive nano silicate of claim 1, wherein:
the reactive nano silicate exhibits UV blocking properties.
8. The reactive nano silicate of claim 1, wherein:
the reactive nano silicate exhibits weather resistant properties.
9. The reactive nano silicate of claim 1, wherein:
the reactive nano silicate is reactive with a polymer.
10. The reactive nano silicate of claim 1, wherein:
the reactive nano silicate is reactive with a hydroxylated material.
11. The reactive nano silicate of claim 1, wherein:
the reactive nano silicate is reactive with a hydroxylated nano carbon.
12. The reactive nano silicate of claim 1, wherein:
the reactive nano silicate is reactive with a hydroxylated nano carbon that comprises at least one of a surface modified carbon black, carbon nano tube, fullerene, thin film graphene, graphene oxide, reduced graphene oxide, graphene nano platelet, graphene hybrid composite, a water soluble GHC, and an engraved GHC.
13. The reactive nano silicate of claim 1, wherein:
the reactive nano silicate is used as a precursor to provide a reinforcement capability of graphene in rubber, wherein the reinforcement capability of graphene in rubber in GHC/RNS is a low temperature cure effect.
14. The reactive nano silicate of claim 1, wherein:
the reactive nano silicate is used as a precursor to enhance thermal conductivity of graphene in media.
15. The reactive nano silicate of claim 1, wherein:
the reactive nano silicate is used as a precursor to enhance thermal conductivity of graphene in boron nitride.
16. The reactive nano silicate of claim 1, wherein:
the reactive nano silicate is used as a precursor to enhance thermal conductivity of graphene in aluminium nitride.