TWI631079B - Method for preparation of rubidium cesium tungsten bronze particles and composition thereof - Google Patents

Abstract

The present invention provides a method for producing bismuth tungsten bronze particles and a composition thereof, and the bismuth tungsten bronze particles (Rb _x Cs _y ) _0.33 WO _z of the present invention is a tungsten oxide material of an alkali gold group metal, and the particles can be used as a near Infrared (NIR) absorber or thermal mask additive; and used in thermosetting resins, sputtered palladium, etc.; the additive is used in organic or inorganic substrates such as plastics, coatings, enamels, inks, adhesives, ceramics or In the glass; the additive is for example the inventor of the plasma torch.

Description

Method for producing bismuth tungsten bronze particles and composition thereof

The present invention relates to a method for producing bismuth tungsten bronze particles and a composition thereof, the present invention relates to bismuth tungsten bronze particles; the particles are nano granules; the particles can be used as near infrared ray (NIR) absorbers or thermal mask additives The granule is applied to a sputtered palladium material, a thermosetting resin; the additive is used in an organic or inorganic substrate such as a plastic, a coating, an enamel, an ink, a binder, a ceramic or a glass; the additive is prepared, for example, by a plasma torch inventor.

According to the known, NIR absorption can be achieved by reducing the oxygen content of tungsten oxide (WO ₃ ). This tungsten oxide by exposure to the reducing atmosphere at elevated temperature to form a tungsten Magneli phase suboxide WO ₃ -x) is achieved. NIR absorption can also be achieved by adding a positive ion ternary to WO ₃ under reducing conditions, which results in a tungsten bronze structure. For example, potassium tungsten bronze and tantalum tungsten bronze are known per se.

Nanoscale tungsten oxide particles are disclosed by J. Am. Ceram. Soc. 90 [12], 4059-4061 (2007).

U.S. Patent No. 2005/0271566 discloses nanoparticle comprising tungsten.

US 2008/0308755 discloses polyester fibers containing Cs _0.33 WO ₃ particles.

A light absorbing resin composition for laser welding is disclosed in U.S. Patent Application Publication No. 2008/0116426.

Therefore, how to develop an innovative structure that is more ideal and practical, and to use the eagerly awaited by consumers, is also the goal and direction of the relevant industry to strive to develop breakthroughs. In view of this, the creator has been engaged in the manufacturing development and design experience of related products for many years. After detailed design and careful evaluation of the above objectives, the present invention has finally become practical.

That is, the main object of the present invention is to provide a method for producing bismuth tungsten bronze particles and a composition thereof; thereby, by innovative and unique design, the present invention can be used as a near infrared ray (NIR) according to the prior art. Absorbent or thermal mask additive; for use in organic or inorganic substrates such as plastics, coatings, enamels, inks, adhesives, ceramics or glass; practical advancement of the additive, for example by plasma torch preparation .

Fig. 1 is a view showing the UV-VIS-IR spectrum of a transparent heat-insulating film according to Examples 1, 2, 3 and 4 of the present invention.

The invention provides a method for manufacturing bismuth tungsten bronze particles, wherein the bismuth tungsten bronze particles have the formula: (Rb _x Cs _y ) _0.33 WO _z , wherein Rb is a ruthenium metal element, Cs is a ruthenium metal element, and W is tungsten. O is oxygen and x+y 1,2 z 3, the bismuth tungsten bronze particles are a powder mixture containing 1 mol of tungsten, 0.01 mol to 5 mol of lanthanum, and 0.05 mol to 0.5 mol of lanthanum, and the powder mixture is manufactured according to the method (Rb _x Cs) _y ) _0.33 WO _z material was subjected to a nano-milling process to form a (Rb _x Cs _y ) _0.33 WO _z powder having a particle diameter of less than 100 nm.

Further, the present invention provides a composition of cerium tungsten bronze particles comprising an organic or inorganic substrate and cerium tungsten bronze particles having the formula (Rb _x Cs _y ) _0.33 WO _z incorporated therein, wherein x+y 1,2 z 3, wherein the substrate is a coating, a plastic, an ink, a binder, a ceramic, a glass or an enamel; preferably, the substrate is a near infrared (NIR) curable coating composition; preferably, a plastic composition in the form of a sheet, sheet or film, and wherein the substrate is selected from the group consisting of polycarbonate, polymethyl methacrylate, polyethylene terephthalate, acrylonitrile butadiene styrene , polyvinylidene fluoride, styrene-acrylonitrile, polyamide, polystyrene, polybutylene terephthalate, polyurethane, polyvinyl butyral, polyvinyl chloride, polypropylene, polyethylene and their Blends, alloys and copolymers; preferably comprising an organophosphorus stabilizer, a hindered phenol antioxidant, a hydroxylamine, a hindered amine light stabilizer, a hydroxyphenylbenzotriazole or a hydroxyphenyl triazine UV Other additives for absorbents and other inorganic or organic NIR absorbers.

Further, the bismuth tungsten bronze particles of the present invention are used as a near infrared ray (NIR) absorber, a heat mask additive, a thermosetting resin or a sputter plated material.

[Example 1]

A transparent heat insulating material having a molar ratio of Rb:Cs:W=0.0066:0.3234:3 was prepared. 10 g of ammonium metatungstate (manufactured and sold by Sigma-Aldrich) was placed in an aqueous solution and stirred to obtain a transparent liquid A1. 2.17 g of cesium carbonate (manufactured by Alfa Aesar) and 0.031 g of cesium carbonate (manufactured by Alfa Aesar) were mixed into an aqueous solution and stirred uniformly to obtain a transparent liquid B1. Further, the liquid B1 was dropped into the liquid A1, and the mixture was uniformly stirred to obtain a transparent mixed liquid C1. The mixed liquid C1 was heated at 180 ° C to obtain a white powder starting material. This initial product was placed under a 10 vol% hydrogen/argon atmosphere and reduced at 600 ° C for 60 minutes as a blue powder.

The blue powder was added to a dispersant (manufactured by BYK) having a weight of 50% by weight based on the weight of the powder, and was dispersed by grinding with 2 mm of zirconium beads to obtain a nano dispersion D1. This dispersion D1 was made into an insulating coating E1 with an acrylic resin. This heat-insulating paint E1 was applied onto a glass substrate and dried at 80 ° C for half an hour to obtain a transparent heat-insulating thin coating film. The results were tested by UV-VIS-IR spectroscopy and the results are shown in Figure 1.

[Example 2]

A transparent heat insulating material having a molar ratio of Rb:W=0.33:3 was prepared. 10 g of ammonium metatungstate (manufactured and sold by Sigma-Aldrich) was placed in an aqueous solution and stirred to obtain a transparent liquid A1. 1.57 g of cesium carbonate (manufactured by Alfa Aesar) was placed in an aqueous solution and stirred uniformly to obtain a transparent liquid B1. Further, the liquid B1 was dropped into the liquid A1, and the mixture was uniformly stirred to obtain a transparent mixed liquid C1. The mixed liquid was heated at 180 ° C with a white powder starting material. This initial product was heated at 600 ° C for 60 minutes under a 10 vol% hydrogen/argon atmosphere. The blue powder was added to a powder having a weight of 50% by weight relative to the weight of the powder (manufactured by BYK), and dispersed by a 2 mm cerium-zirconium bead to obtain a nano-dispersed liquid D1. This dispersion D1 was made into an insulating coating E1 with an acrylic resin. This heat-insulating paint E1 was applied onto a glass substrate and dried at 80 ° C for half an hour to obtain a transparent heat-insulating thin coating film. The results were tested by UV-VIS-IR spectroscopy and the results are shown in Figure 1.

[Example 3]

A transparent heat insulating material having a molar ratio of Rb:Cs:WO=0.165:0.165:0.33 was prepared. 10 g of ammonium metatungstate (manufactured and sold by Sigma-Aldrich) was placed in an aqueous solution and stirred to obtain a transparent liquid A1. 1.1 g of cesium carbonate (produced by Alfa Aesar) and 0.79 g of cesium carbonate (produced by Alfa Aesar) A 50 wt% aqueous solution was stirred uniformly to obtain a transparent liquid B1. Further, the liquid B1 was dropped into the liquid A1, and the mixture was uniformly stirred to obtain a transparent mixed liquid C1. The mixed liquid was heated at 180 ° C to give an initial product as a white powder. This initial product was heated at 600 ° C for 60 minutes under a 10 vol% hydrogen/argon atmosphere. The blue powder was added to a powder having a weight of 50% by weight relative to the weight of the powder (manufactured by BYK), and dispersed by a 2 mm cerium-zirconium bead to obtain a nano-dispersed liquid D1. This dispersion D1 was made into an insulating coating E1 with an acrylic resin. This heat-insulating paint E1 was applied onto a glass substrate and dried at 80 ° C for half an hour to obtain a transparent heat-insulating thin coating film. The results were tested by UV-VIS-IR spectroscopy and the results are shown in Figure 1.

[Embodiment 4]

A transparent heat insulating material having a molar ratio of Rb:Cs:W=0.033:0.297:3 was prepared. 10 g of ammonium metatungstate (manufactured and sold by Sigma-Aldrich) was formulated into a 30 wt% aqueous solution, and stirred uniformly to obtain a transparent liquid A1. 1.98 g of cesium carbonate (manufactured by Alfa Aesar) and 0.157 g of cesium carbonate (manufactured by Alfa Aesar) were mixed into a 50 wt% aqueous solution, and stirred uniformly to obtain a transparent liquid B1. Further, the liquid B1 was dropped into the liquid A1, and the mixture was uniformly stirred to obtain a transparent mixed liquid C1. The mixed liquid was heated at 180 ° C to give an initial product as a white powder. The blue powder was added to a powder having a weight of 50% by weight relative to the weight of the powder (manufactured by BYK), and dispersed by a 2 mm cerium-zirconium bead to obtain a nano-dispersed liquid D1. This dispersion D1 was made into an insulating coating E1 with an acrylic resin. This heat-insulating paint E1 was applied onto a glass substrate and dried at 80 ° C for half an hour to obtain a transparent heat-insulating thin coating film. The results were tested by UV-VIS-IR spectroscopy and the results are shown in Figure 1.

It can be seen from the comparison of the thermal insulation performance indexes of the transparent heat-insulating films of Examples 1 to 4 that the heat insulating performance of the transparent heat-insulating film containing the alkali gold-group metal oxide powder is higher than that of the alkali metal-containing metal. Transparent heat-insulating film of miscellaneous tungsten oxide powder.

In summary, the transparent heat insulating material (Rb _x Cs _y ) _0.33 WO _z of the present invention is an alkali gold metal tungsten oxide material, and the transparent heat insulating film made of the transparent heat insulating material can simultaneously have high Visible light transmittance and high infrared ray rejection, and can be made into a film using a low-cost wet coating method.

Although the present invention has been disclosed in its preferred embodiments, it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application attached.

By summarizing the above description, the design of the above structure of the present invention can effectively overcome the conventional invention The present invention has been developed as an innovative invention, and the same or similar product creation or public use has not been seen in the same technical field, so the present invention has been The requirements for the "novelty" and "progressiveness" of the invention patents are submitted in accordance with the law.

Claims (2)

A method for producing bismuth tungsten bronze particles, such as: (Rb _x Cs _y ) _0.33 WO _z ; wherein Rb is a ruthenium metal element, Cs is a ruthenium metal element, W is tungsten, O is oxygen, and x+y 1,2 z 3. The method comprises performing a nano-milling process on the (Rb _x Cs _y ) _0.33 WO _z material, wherein the powder mixture contains ruthenium based on 1 mol of tungsten, 0.01 mol to 5 mol, and 0.05 mol to 0.5 mol of ruthenium , 俾 forms a (Rb _x Cs _y ) _0.33 WO _z powder having a particle diameter of less than 100 nm; the bismuth tungsten bronze particles are used as a near-infrared (NIR) absorber, a thermal mask additive, a thermosetting resin, and a sputtered palladium The use of materials. A composition of cerium tungsten bronze particles comprising an organic or inorganic substrate and cerium tungsten bronze particles having the formula (Rb _x Cs _y ) _0.33 WO _z incorporated therein, wherein x+y 1,2 z 3, wherein the substrate is a coating, a plastic, an ink, a binder, a ceramic, a glass or an enamel, wherein the substrate is a near-infrared (NIR)-curable coating composition in the form of a sheet, sheet or film. Plastic composition, and wherein the substrate is selected from the group consisting of polycarbonate, polymethyl methacrylate, polyethylene terephthalate, acrylonitrile-butadiene-styrene, polyvinylidene fluoride, styrene - acrylonitrile, polyamide, polystyrene, polybutylene terephthalate, polyurethane, polyvinyl butyral, polyvinyl chloride, polypropylene, polyethylene and blends, alloys and copolymers thereof It comprises an organic phosphorus stabilizer, a hindered phenol antioxidant, a hydroxylamine, a hindered amine light stabilizer, a hydroxyphenylbenzotriazole or a hydroxyphenyl triazine UV absorber, and other inorganic or organic NIR absorbers. Additive; the bismuth tungsten bronze particles can be used as a near-infrared (NIR) absorber, a heat mask additive, a thermosetting resin, and a sputter-plated material.