AT515869A1 - Production process of nanoneedle-shaped purple tungsten oxide for the industry - Google Patents

Abstract

The invention relates to a method of producing nanoneedle-shaped magenta tungsten oxide which uses 5 (NH 4) 2 O. 12WO 3 .5Hz 0, mWO 3 .nHzO (m-1, n-1) or WOx (2: s_x.:s_3) as material and in one rotated oblique stovepipe is performed. The material is fed from the material feed device through the material inlet opening at the material outlet side in the heated stovepipe, wherein the material is moved from the low-temperature zone to the high-temperature zone by rotating the inclined stovepipe. The material is reduced in the high-temperature zone, thereby producing the needle-shaped purple W02, 72 which is moved to the material exit side by rotating the inclined furnace tube, exiting through the material exit port, and cooled to room temperature. This allows for mass production of the nanoparticle magenta tungsten oxide.

Description

Technical area

The invention relates to a manufacturing method of nanoneedle-shaped purple tungsten oxide for the industry.

State of the art

Nanowolframpulver (particle size <100 nm) and

Ultrafine tungsten powder (100 nm <particle size <500 nm) is an important material for the production of nano tungsten carbide (particle size <100 nm), ultrafine tungsten carbide (100 nm <particle size <500 nm) and ultrafine hard alloy (100 nm <particle size &lt; 500nm). Nano tungsten carbide, ultrafine wolves carbide and ultrafine hard alloy are higher value added products in the international market.

The technique, which uses nanoparticle magenta tungsten oxide (WO2,72) as a material and utilizes Rayleigh instability and in situ oxygen reduction, is a good method of making nanoflow ampoules and ultrafine tungsten powders. The nano-needle purple tungsten oxide (W02, 72) is a functional nanomaterial and has many properties, such as photochromic, electrochromic and gastric properties, and can be applied to various sensitive devices.

Therefore, the nanoneedle-shaped purple tungsten oxide has a high value and needs in the market. However, a manufacturing method of the nanoparticle magenta tungsten oxide for mass production has not been known hitherto. For this reason, the inventor has developed the present invention.

Object of the invention

The invention has for its object to provide a manufacturing method of nanoneedle purple tungsten oxide for the industry.

This object is achieved by the production process of nanoparticle magenta tungsten oxide according to the invention using 5 (NH 4) 2 O.I 2 WO 3 5H 2 O, mWO 3 -nH 2 O (m> 1, n> 1) or W0X (2 <x <3) as material and in one rotated oblique stovepipe is performed. The material is fed from the material feed device through the material inlet opening at the material outlet side in the heated stovepipe, wherein the material is moved from the low-temperature zone to the high-temperature zone by rotating the inclined stovepipe. The material is reduced in the high temperature zone, thereby producing the acicular purple W02, 72, which is moved by rotating the inclined furnace tube to the material exit side, exiting through the material exit port, and cooled to room temperature.

Teaching of the invention: (1)

As material 5 (NH4) 20-12W03 · 5Η20 is used.

When 5 (NH 4) 2O-12WO 3 -5H 2 O is heated above 400 ° C, the reaction of Formula (1) occurs to produce WO 3, NH 3 and H 2 O.

(1)

The reaction product NH 3 of the formula (1) or the introduced NH 3 generates the reaction of the formula (2) under catalyzation by W 0 X (2 <x <3), thereby obtaining the reductive hydrogen gas H 2.

(2)

When the reaction temperature rises above 500 ° C, the yellow reaction product W03 of the formula (1) with the reaction product H2 of the formula (2) and / or the introduced H2 generates the reduction reaction of the formula (3), whereby blue-colored WO 2 (9 and H20 is obtained.

(3)

When the reaction temperature rises above 600 ° C, the blue-colored reaction product WO 2, g of the formula (3) with the reaction product H 2 of the formula (1) and / or the introduced H 2 generates the reduction reaction of the formula (4), whereby purple WO 2, 72 and H20 is obtained.

(4)

In formulas (1), (3) and (4), water vapor H 2 O is generated.

Under the high temperature, H 2 O and WO x (2 <x <3) produce a reversible reaction of formula (5) to give WO 2 (0H) 2. W02 (OH) 2 is a gas at high temperature.

(5)

Due to the phase shift of W02 (OH) 2, the purple W02 / 72 crystal nucleus of the formula (4) can grow to the nanochar purple W02.72 crystal.

The stovepipe has a gas outlet opening. An exhaust fan on the outside of the gas outlet port controls the gas outlet speed of the stovepipe to maintain the positive pressure in the stovepipe at Ombar - 5mbar. The nanoneedle-shaped purple W02.72 crystal has a diameter of less than 100 nm and belongs to the nanomaterial. (2)

The material used is mW03 · ηΗ20, where m> 1, n> 1.

When mW03 · ηΗ20 is heated above 100 ° C, the reaction of the formula (6) occurs to generate WO 3 and H 2 O.

(6)

NH3 is introduced through the gas inlet opening, producing the reaction of formula (2) under the catalysis by WOx (2 <x <3), thereby obtaining the reductive hydrogen gas H2.

When the reaction temperature rises above 500 ° C, the yellow colored reaction product WO 3 of the formula (6) with the reaction product H 2 of the formula (2) produces the reduction reaction of the formula (3) to obtain blue-colored W 2 O 3 and H 2 O.

If NH3 is not introduced or the introduced NH3 is not sufficient, gas may be introduced through the gas inlet H2. When the reaction temperature rises above 500 ° C, the yellow colored reaction product W03 of the formula (6) with the reaction product H2 of the formula (2) and / or the introduced H2 generates the reduction reaction of the formula (3), whereby blue-colored W02 / 9 and H20 is obtained.

When the reaction temperature rises above 600 ° C, the blue-colored reaction product WO 2, g of the formula (3) with the reaction product H 2 of the formula (2) produces the reduction reaction of the formula (4) to give magenta W 2 .72 and H 2 O.

If NH3 is not introduced or the introduced NH3 is not sufficient, gas may be introduced through the gas inlet H2. When the reaction temperature rises above 600 ° C, the blue-colored reaction product WO 3 of the formula (3) with the reaction product H 2 of the formula (2) and / or the introduced H 2 generate the reduction reaction of the formula (4), whereby magenta W 2 .72 and H 2 O is obtained.

In the formulas (6), (3) and (4), the water vapor H20 is generated. Under the high temperature, H 2 O and W x O x (2 <x <3) produce a reversible reaction of formula (5) to give WO 2 (0H) 2. W02 (0H) 2 is a gas under high temperature.

Due to the phase shift of W02 (OH) 2, the purple W02j72 crystal nucleus of the formula (4) can grow to the nanochar purple W02.72 crystal.

The stovepipe has a gas outlet opening. An exhaust fan on the outside of the gas outlet port controls the gas outlet speed of the stovepipe to maintain the positive pressure in the stovepipe at Ombar - 5mbar. The nanoneedle-shaped purple W02.72 crystal has a diameter of less than 100 nm and belongs to the nanomaterial. (3)

The material used is W0X (2 <x <3) or WO * (2 <x <3) from the manufacturing process and / or from the reaction product. NH3 and / or H2 are introduced through the gas inlet opening. According to W0 * (2 <x <3), it is decided whether H20 is introduced.

When NH3 is introduced, NH3 generates, under catalyzed by W0X (2 <x <3), the reaction of the formula (2), whereby the reductive hydrogen gas H2 is obtained.

When WO * (2 <x <3) contains the yellow W03 and the reaction temperature rises above 500 ° C, the yellow colored reaction product W03 with the introduced H2 generates the reduction reaction of the formula (3) to obtain blue-colored W02.9 and H20 ,

When the reaction temperature rises above 600 ° C, the blue-colored reaction product W02.9 of the formula (3) with the introduced H2 generates the reduction reaction of the formula (4), thereby obtaining purple W02.72 and H20.

When WO * (2 <x <3) contains the blue-colored W02.9 and the reaction temperature rises above 600 ° C, the blue-colored reaction product W02, g with the introduced H2 generates the reduction reaction according to the formula (3), whereby purple W02 ( 72 and H20 is obtained.

In formulas (3) and (4), water vapor H20 is produced. If H20 of the formulas (3) and / or (4) is insufficient, H20 can be introduced through the gas inlet port. Under the high temperature, H20 of formulas (3) and / or (4) and / or the introduced H20 produce reversible with WOx (2 <x <3)

Reaction of formula (5) to give WC> 2 (OH) 2. W02 (OH) 2 is a gas at high temperature.

By the phase shift of WC &gt; 2 (OH) 2, the purple W02 / 72 crystal nucleus of the formula (4) can grow to the nanochip purple-purple WC &gt; 2.72 crystal.

The stovepipe has a gas outlet opening. An exhaust fan on the outside of the gas outlet port controls the gas outlet speed of the stovepipe to maintain the positive pressure in the stovepipe at Ombar - 5mbar. The nanoneedle-shaped purple WÜ2.72 crystal has a diameter of less than 100 nm and belongs to the nanomaterial.

This allows mass production of nanoneutrous purple tungsten oxide for industry.

Brief description of the drawings

FIG. 1 shows a spectrum of the Co-Target XRD analysis of the product of the first embodiment of the invention,

FIG. 2 is a picture of Hitachi S-4800II cold field scanning electron microscope of the product of the first embodiment of the invention;

FIG. 3 shows a spectrum of the co-target XRD analysis of the product of the second embodiment of the invention,

FIG. 4 is an image of Hitachi S-4800II cold field scanning electron microscope of the product of the second embodiment of the invention;

FIG. 5 is a spectrum of Co-target XRD analysis of the product of the third embodiment of the invention;

Figure 6 is a picture of Hitachi S-480II cold field scanning electron microscope of the product of the third embodiment of the invention.

Ways to carry out the invention

Embodiment 1: the material 5 (NH 4) 2 O. 12WO 3 .5H 2 O is conveyed by the material feeding device through the

Material inlet opening at the material outlet side in the heated furnace tube entered. By rotating the inclined stovepipe, the material is moved from the low temperature zone to the high temperature zone. When 5 (NH 4) 20 .12W 3 .5H 2 O enters the temperature zone of 400 ° C-600 ° C, the reaction of the formula (1) occurs, producing WO 3, NH 3 and H 2 O.

The reaction product W0X (2 <x <3) of the formulas (1), (3) and (4) is a good catalyst for decomposing NH3. In the furnace tube, NH 3 is pyrolytically decomposed according to the formula (2), whereby the reductive hydrogen gas H 2 is generated.

The material is moved by turning the inclined stovepipe further to the high temperature zone. When the temperature of the material rises to 550 ° C-800 ° C, the reaction according to the formula (3) occurs. When the temperature of the material rises to 750 ° C-800 ° C, the reaction of the formula (4) occurs to produce the purple W02j72 crystal nucleus.

In the formulas (1), (3) and (4), the water vapor H20 is generated.

The stovepipe has a gas outlet opening. An exhaust fan on the outside of the gas outlet port controls the gas outlet velocity of the furnace tube to maintain the positive pressure in the furnace tube at 0.2mbar - 2.0mbar.

Under the high temperature, H 2 O and WO x (2 <x <3) produce a reversible reaction of formula (5) to give WO 2 (0H) 2. Due to the phase shift of W02 (0H) 2, the purple W02.72 crystal nucleus of the formula (4) can grow to the nanochip purple W02.72 crystal.

Turning the oblique furnace tube, the nanoneedle purple WO2.72 crystal is further to the

Material exit side moves. The material outlet side of the stovepipe is not heated. When the purple W02, 72 is cooled to near room temperature, it exits through the material exit orifice.

The purple W02, 72 in Embodiment 1 is used as a reagent. The reagent is ground and analyzed with PANalytical X'pert PRO XRD using a Co target that has a sampling step of 0.033 ° and each step lasts for 10 seconds.

FIG. 1 shows the spectrum of the XRD analysis. The reagent is the purple W02.72 with a purer phase.

The purple W02j72 in Embodiment 1 is used as a reagent and observed with Hitachi S-4800II cold field scanning electron microscope. From Figure 2 it can be seen that the nanoclip purple W02.72 crystal has a diameter in the range of 20-80nm and belongs to the nanomaterial.

Embodiment 2: the material mW03 · ηΗ20 (m = l, n = l) is the material feed device by the

Material inlet opening at the material outlet side in the heated furnace tube entered. By rotating the inclined stovepipe, the material is moved from the low temperature zone to the high temperature zone. When WO3 · Η2θ enters the temperature zone of 100 ° C-300 ° C, the reaction of the formula (6) occurs, generating W03 and H20.

NH3 is introduced through the gas inlet, whereby NH3: W03-H2O = 0.5 mol-l, 5 mol: lmol. W0X (2 <x <3) is a good catalyst for decomposing NH3. In the furnace tube, NH 3 is pyrolytically decomposed according to the formula (2), whereby the reductive hydrogen gas H 2 is generated.

The material is moved by turning the inclined stovepipe further to the high temperature zone. When the temperature of the material rises to 550 ° C-800 ° C, the reaction according to the formula (3) occurs. When the temperature of the material rises to 750 ° C-800 ° C, the reaction of the formula (4) occurs to produce the purple W02.72 crystal nucleus.

The stovepipe has a gas outlet opening. An exhaust fan on the outside of the gas outlet port controls the gas outlet velocity of the furnace tube to maintain the positive pressure in the furnace tube at 0.2mbar - 2.0mbar.

Under the high temperature, H 2 O and W x O x (2 <x <3) produce a reversible reaction of formula (5) to give WO 2 (OH) 2. Due to the phase shift of W02 (0H) 2, the purple WO2 / 72 crystal nucleus of formula (4) can grow to the nanochip purple W02; 72 crystal.

By turning the oblique stovepipe, the nanochar-shaped purple W02.72 crystal becomes further to the

Material exit side moves. The material outlet side of the stovepipe is not heated. When the purple W02> 72 is cooled to near room temperature, it exits through the material exit port.

The purple W02 / 72 in Embodiment 2 is used as a reagent. The reagent is ground and analyzed with PANalytical X'pert PRO XRD using a Co target that has a sampling step of 0.033 ° and each step lasts for 10 seconds.

FIG. 3 shows the spectrum of the XRD analysis. The reagent is the purple W02.72 with a purer phase.

The purple W02, 72 in Embodiment 2 is used as a reagent and observed with Hitachi S-480II cold field scanning electron microscope. From Figure 4 it can be seen that the diameter of the nanochip purple W02.72 crystal is in the range of 20-80cm and belongs to the nanomaterial.

Embodiment 3: the yellow-colored material WO3 is fed by the material feed device through the

Material inlet opening at the material outlet side in the heated furnace tube entered. By rotating the inclined stovepipe, the material is moved from the low temperature zone to the high temperature zone.

NH3 and H 2 O are introduced through the gas inlet opening, NH 3: WO 3 = 0.5 mol-1, 5 mol: 1 mol and H 2 O: WO 3 = 0, 1 mol-0.6 mol: 1 mol. W0X (2 <x <3) is a good catalyst for decomposing NH3. In the furnace tube, NH 3 is pyrolytically decomposed according to the formula (2), whereby the reductive hydrogen gas H 2 is generated.

The material is moved by turning the inclined stovepipe further to the high temperature zone. When the temperature of the material rises to 550 ° C-800 ° C, the reaction according to the formula (3) occurs. When the temperature of the material rises to 750 ° C-800 ° C, the reaction of the formula (4) occurs, thereby producing the purple W02 / 72 crystal nucleus.

The stovepipe has a gas outlet opening. An exhaust fan on the outside of the gas outlet port controls the gas outlet velocity of the furnace tube to maintain the positive pressure in the furnace tube at 0.2mbar - 2.0mbar.

Under the high temperature, H 2 O and W x O x (2 <x <3) produce a reversible reaction of formula (5) to give WO 2 (0H) 2. Due to the phase shift of W02 (0H) 2, the purple W02.72 crystal nucleus of the formula (4) can grow to the nanochip purple W02,? 2 crystal.

By turning the oblique stovepipe, the nanochar-shaped purple W02 / 72 crystal continues to become the

Material exit side moves. The material outlet side of the stovepipe is not heated. When the purple W02 (72 is cooled to near room temperature, it exits through the material exit orifice.

The purple W02, 72 in Embodiment 3 is used as a reagent. The reagent is ground and analyzed with PANalytical X'pert PRO XRD using a Co target that has a sampling step of 0.033 ° and each step lasts for 10 seconds.

Figure 5 shows the spectrum of XRD analysis. The reagent is the purple WÜ2,72 with a purer phase.

The purple W02, 72 in Embodiment 3 is used as a reagent and observed with Hitachi S-4800II cold field scanning electron microscope. From Figure 6 it can be seen that the diameter of the nanochip purple W02.72 crystal is in the range of 20-80cm and belongs to the nanomaterial.

Claims (18)

Claims 1. A method of producing nanoradical magenta tungsten oxide using 5 (NH 4) 20 .12WO 3 .5H 2 O as a material and comprising the steps of: A: the material 5 (NH 4) 2 O.I 2WO 3 .5H 2 O is passed through the material inlet opening at the material feed device Entered material outlet side in the heated stovepipe, wherein the material is moved from the low-temperature zone to the high-temperature zone by turning the inclined stovepipe; B: 5 (NH4) 20-12W03-5H20 is pyrolytically decomposed to produce WO 3, NH 3 and H 2 O; C: NH3 is pyrolytically decomposed in the furnace tube, producing the reductive hydrogen gas H2; and D: the material is further moved to the high temperature zone by rotating the inclined stovepipe, whereby WO3 is reduced by H2, producing the purple W02, 72. 2. Production method according to claim 1, characterized in that NH3 and / or H2 is introduced through the gas inlet opening of the furnace tube. 3. A manufacturing method according to claim 1, characterized in that the heating temperature of 5 (NH4) 20 -12W03-5H20 is above 400 ° C. A production process according to claim 1, characterized in that the reaction temperature of the magenta WC is> 2.72 above 600 ° C. 5. A manufacturing method according to claim 1, characterized in that the furnace tube has a gas outlet opening, wherein the gas outlet of the furnace tube is controlled by an exhaust fan on the outside of the gas outlet opening to maintain the positive pressure in the furnace tube to Ombar - 5mbar. 6. A method of producing nanoparticle magenta tungsten oxide using mW03 · ηΗ20 as a material, wherein m> 1 and n> 1, and comprising the steps of: A: the material mW03-nH20 is introduced into the material exit side from the material supply port through the material inlet port heated stovepipe is entered, wherein by rotating the inclined stovepipe, the material is moved from the low-temperature zone to the high-temperature zone; B: mWO 3 -nH 2 O is pyrolyzed to produce WO 3 and H 2 O; and C: the material is moved further to the high temperature zone by rotating the oblique furnace tube, whereby W03 is reduced by H2, producing the purple W02, 72. 7. A manufacturing method according to claim 6, characterized in that NH3 is introduced through the gas inlet opening of the furnace tube, wherein in the furnace tube NH3 is pyrolytically decomposed, whereby the reductive hydrogen gas H2 is generated. 8. A manufacturing method according to claim 6, characterized in that in the furnace tube and H2 or the mixture of H2 and NH3 is introduced. 9. Production method according to claim 6, characterized in that the heating temperature of mW03 -nH20 is above 100 ° C. 10. A manufacturing method according to claim 6, characterized in that the reaction temperature of the purple W02 / 72 is above 600 ° C. 11. A manufacturing method according to claim 6, characterized in that the furnace tube has a gas outlet opening, wherein the exhaust gas outlet of the furnace tube is controlled by an exhaust fan on the outside of the gas outlet opening to maintain the positive pressure in the furnace tube to Ombar - 5mbar. 12. A method of producing nanoparticle magenta tungsten oxide using WOx as a material, wherein 2 <x <3, and comprising the steps of: A: the material WOx is fed from the material feeder through the material inlet at the material exit side into the heated furnace tube Rotating the inclined stovepipe, the material is moved from the low temperature zone to the high temperature zone; and B: the material is further moved to the high temperature zone by rotating the inclined stovepipe, whereby WOx is reduced by H2, producing the purple W02, 72. 13. A manufacturing method according to claim 12, characterized in that NH3 is introduced through the gas inlet opening of the furnace tube, wherein NH3 is pyrolytically decomposed in the furnace tube, whereby the reductive hydrogen gas H2 is generated. 14. A manufacturing method according to claim 12, characterized in that H2 or the mixture of H2 and NH3 is introduced through the gas inlet opening of the furnace tube. 15. A manufacturing method according to claim 12, characterized in that H20 is introduced through the gas inlet opening of the furnace tube. 16. Production process according to claim 12, characterized in that the reaction temperature of the magenta W02 (72 is above 600 ° C. 17. A manufacturing method according to claim 12, characterized in that the furnace tube has a gas outlet opening, wherein the exhaust gas outlet speed of the furnace tube is controlled by an exhaust fan on the outside of the gas outlet opening to maintain the positive pressure in the furnace tube to Ombar - 5mbar. Vienna, am June 18, 2013 Xiamen Golden Egret Special Alloy Co., Ltd. by: Haffner and Keschmann Patentanwälte GmbH