WO2005063629A1 - Synthesis of ultrafine rutile phase titanium dioxide particles at low temperature - Google Patents
Synthesis of ultrafine rutile phase titanium dioxide particles at low temperature Download PDFInfo
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- WO2005063629A1 WO2005063629A1 PCT/IN2003/000429 IN0300429W WO2005063629A1 WO 2005063629 A1 WO2005063629 A1 WO 2005063629A1 IN 0300429 W IN0300429 W IN 0300429W WO 2005063629 A1 WO2005063629 A1 WO 2005063629A1
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- titanium dioxide
- phase
- ticl
- rutile
- dopant
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/07—Producing by vapour phase processes, e.g. halide oxidation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Definitions
- the present invention relates to a low temperature process for the synthesis of ultrafine rutile phase titanium dioxide particles through vapor phase hydrolysis of titanium tetra chloride.
- the present invention relates to a method for the manufacture of rutile grade titanium dioxide powder using ethanol as dopant to bring down the rutile formation temperature to as low as 150 - 400°C during calcination with time duration of 1 to 4 hrs.
- the process includes a novel combination of operational steps to economically produce ultrafine titanium dioxide powders of rutile phases in a flexible manufacturing process.
- Titanium dioxide (titania) is extensively used as pigments, catalysts, inorganic membranes, semi-conductors, optical coating reagent and as photocatalysts in water purification process.
- Titanium dioxide (TiO 2 ) has two phases of crystalline structure of industrial importance, namely, anatase and rutile. Titanium dioxide with anatase phase has been used as a photocatalyst for photodecomposition of acetone, phenol or trichloro ethylene, oxidation such as nitrogen mono-oxide and hitrogen dioxide and conversion system using solar energy due to its high photo-activity. Titanium dioxide with rutile phase has been widely used as white pigment because of its good scattering effect that protects the ultraviolete light.
- Titanium dioxide shows different electrical characteristics according to oxygen partial pressure since it has wide chemical stability and non-stoichiometric phase region. Because of this, it can also be used as a humidity sensor and as high-temperature oxygen sensor and the field of its use has become wide. Titanium dioxide powders for pigment use generally have an average particle size of 150 to 250 nanometer and is considered the principal white pigment of commerce. It has an exceptionally high refractive index, negligible color and is quite inert.
- Titanium dioxide is having a smaller average particle size, for instance in the 10 to 100 nanometer median particle size range, is used commercially in cosmetics and personal care products, plastics, surface coating, self - cleaning surfaces, and photo voltaic applications. This grade of titanium dioxide is referred to as ultrafine or nano-sized titanium dioxide. More than four million tons of titanium dioxide are produced annually; there are several processes for making ultrafine titanium dioxide, some in commercial use and some in development. Some use anhydrous titanium dioxide, some in commercial use and some in development. Some use anhydrous titanium tetrachloride as a feed stock. Another process use a titanyl sulfate solution as the feed stock.
- titanium dioxide powders are manufactured by a chloride process, which is a gas phase process, or by a sulfate process, which is a hquid phase process.
- chloride process which was commercialized by Du Pont of USA in 1956, titanium tetrachloride, is used as a starting material and the reaction temperature needs to be higher than 1,000°C. This method also requires extra protection devices because of the corrosive Cl 2 gas product at high temperature in the process, leading to higher production costs.
- titanium dioxide powders produced by the chloride process are fine but rough, additive equipment for providing external electrical fielfs or controlling reactant mixing ratios are required to control the particle shape and the particle size of titanium dioxide powders. High pure oxygen is required for oxidation of TiCl 4 and that leads to high capital and operating costs.
- sulfate process which was commercialized by Titan company of Norway in
- titanium sulfate (TiSO 4 ) is conventionally hydrolyzed at temperatures higher than 100°C, calcined at 800 - 1000°C and then pulverised to produce titanium dioxide powders. During the calcination and pulverization processes, impurities are introduced causing the quality of the final titanium dioxide powder to be low. Funaki, Saeki, et al. in Kogyo Kagaku Zasshi, 59 (11), pp.
- fine particles of anatase-type titanium dioxide can be produced by mixing titanium tetrachloride and water in the vapor phase at a temperature in the range from 200°C to 800°C or fine particles of anatase-type titanium dioxide containing or not containing a very small amount of rutile-type particles can be produced by the reaction of titanium tetrachloride and water in the liquied phase and a much higher temperature treatment to obtain rutile phase titanium dioxide.
- a method for preparing spherical particles of a metal oxide comprising hydroysis of a hydrolysable titanium (IV) compound in the form of a liquid aerosol by being contacted with water vapor in a dynamic flow is taught in US Patent 4,241,042.
- a method in which a precursor of a metal oxide in the form of a very fine droplet suspension of the hquid is heated and gasified by evaporation and thermal decomposition and then contacted and reacted with an oxygen containing gas in the vapor phase to give spherical fine particles of a metal oxide is taught in Japanese Patent Kokai 59-107904 and 59-107905.
- Recently considerable interest has been directed toward the synthesis of rutile grade titania at low temperature.
- the main objective of the invention is to develop a low temperature process for the synthesis of ultrafine rutile particles through vapor phase hydrolysis of TiCl 4 .
- Another object of the present invention is to develop a flexible low temperature process for the synthesis of anatase, rutile and mixtures thereof in the same reactor system.
- the present invention provides a low temperature process for the synthesis of ultrafine rutile phase titanium dioxide particles through vapor phase hydrolysis of titanium tetrachloride comprising the step of: a) hydrolyzing a mixture of TiCl 4 and H 2 O and a dopant in vapour phase in an aerosol reactor; b) collecting amorphous or anatase titanium dioxide powder formed as dry powders; c) calcining the dry powder to obtain rutile phase titanium dioxide.
- the amorphous particles of titanium dioxide are calcined at a temperature in the range of 150 to 400°C and for a period in the range of 1 to 4 hrs to generate rutile particles.
- the dopant contains a carbon atom and is selected from the group consisting of an aliphatic alcohol, an aromatic hydrocarbon, and any mixture thereof.
- the dopant is ethanol.
- the molar concentration of the dopant is 1 to 10 based on the water vapour.
- the reaction mixture contains from 0 to 10 % ethanol on a molar basis based on TiCl 4 .
- the flow rate of TiCl 4 is in the range of 10 cm 3 /min to 200 cm 3 /min.
- the TiCl 4 vapor concentration inside the reactor is in the range of 7 x 1 O ⁇ mol/min to 1 x 10 ⁇ 2 moiVmin.
- the flow rate of water vapour is in the range of 240 to 1500 cm 3 /min, preferably from 500 to 1000 cm 3 /min.
- temperature at the exit of the aerosol reactor is maintained at less than 100°C for obtaining titanium dioxide particles having anatase phase.
- the aerosol reactor is externally heated in order to avoid particle coating on the walls through thermophoresis.
- the aerosol reactor consists of 3 - tube concentric jet assembly wherein TiCl 4 is introduced into the innermost tube, dopant is introduced into the outermost tube and water vapor is introduced into the middle tube.
- the 3 -tube assembly comprises a concentric arrangement of three inconel tubes at the entrance of the aerosol reactor.
- the vapor phase TiCl 4 is introduced into a center tube of the three concentric inconel tubes.
- the vapor phase TiCl is formed by bubbling an inert gas through TiCl 4 liquid.
- the -inert gas is selected from the group consisting of argon, nitrogen, krypton, helium and any mixture thereof.
- the molar ratio of water to titanium tetra chloride in the feed is in the range 10 to 15.
- the water vapor is formed by bubbling air or inert gases through water under superheated condition.
- the reactor wall temperature is from 200 to 450°C.
- the rutile titanium dioxide particles formed have an average diameter in the range of from 25 to 150 nanometers.
- the present invention also provides a low temperature process for the synthesis of ultrafine rutile phase titanium dioxide particles through vapor phase hydrolysis of titanium tetrachloride comprising the step of: a. vaporizing a titanium chloride liquid, water and a dopant comprising ethanol separately to generate a reaction mixture ; b. hydrolyzing vapor phase TiCl 4 and H O and dopant mixture in a continuous aerosol reactor under non-isothermal conditions at a temperature in the range of 80 to 135°C; c. collecting amorphous and anatase phase titanium dioxide powder as dry powder; d.
- FIG. 1 represents a flow sheet of the general aspect of the rutiel phase titanium dioxide synthesis using low temperature vapore phase process according to the present invention.
- Figure 2 represents a layout of nozzle inlet assembly for mixing of reactants of reactants and dopant in the inlet part to the reactor.
- the present invention relates to a gas phase based aerosol synthesis of rutile phase titanium dioxide particles at a much lower temperature so as to avoid the several unit operations for the treatment of large hquid volumes and non-requirement of a need for high purity oxygen as in the chloride process.
- the present invention has successfully led high purity oxygen as in the chloride process.
- the present invention has successfully led to the development of to new titanium dioxide powder manufacturing method. In this method, it is possible to prepare ultrafine titanium dioxide powders of rutile phase continuously with excellent control of particle characteristics such s particle shase, particle size, and specific crystallographic modifications.
- This invention also provides a low temperature, low cost, environmentally friendly flexible process for preparing titanium dioxide powders.
- the present invention relates to a process for the synthesis of titanium dioxide powders having rutile phase by TiCl 4 hydrolysis in vapor phase followed by low temperature calcination.
- the process defined herein consists of three basis steps: (1) Hydrolyzing a reactant mixture containing TiCl 4 vapor, water vapor and optionally, a dopant in a vapour phase reactor. (2) Collecting titanium dioxide powder having amorphous phase formed inside the vapor phase reactor. (3) Low temperature calcination of the collected powder. The precise details of these steps are set forth below.
- the hydrolyzing reaction takes place in the aerosol reactor of LO 2.5 cm and 1.5m in length, heated externally in a horizontal electrical furnace (Fig. 1).
- the reactor comprises of a metallic tube made of Inconel in which the reactants (TiCl 4 , H 2 O, and the dopant) are introduced as vapor.
- the aerosol reactor consists of three concentric Inconel tubes as shown in Fig. 2. the inner diameter of the central tube is 2mm and the spacing between successive tubes is 1mm respectively.
- the mixture of TiCl vapor and nitrogen is introduced through the concentric inconel tube (a), water vapor is introduced through the tube (b) and dopant vapor is introduced into the system through the concentric inconel tube (c).
- the TiCl 4 reactant is introduced into the reactor in the vapor phase.
- TiCl vapor can be generated by bubbling an inert gas through liquid TiCl 4 , the nitrogen gas/ TiCl 4 vapor is preferably directed through the concentric inconel tube (a) of the reactor.
- the TiCl 4 flow rates utilized in the process of the present invention are generally from about 10 cm 3 /min to about 200 cm 3 /min. This flow rate (together with the liquid TiCl 4 temperature) essentially define the concentration of TiCl , which is present inside the reactor.
- the TiCl 4 vapor concentration ranges inside the reactor, which are useful in the present invention, are from about 7 x lO ⁇ mol/min to about 1 x 10 ⁇ 2 mol/min.
- Heating the TiCi 4 liquid through which the nitrogen gas is bubbled controls the actual concentration of TiCl vapor in the nitrogen gas.
- the TiCl 4 through which the nitrogen is bubbled has a temperature of from about 20°C to about 100°C.
- the other required reactant utilized in the process of the invention is water vapor. Water vapor is generated by bubbling air through water and directing that gas (air with water vapor) into the reactor through the concentric inconel tube (b). This procedure allows for precise control of water vapour flow rate and concentration in the reactor.
- the air (containing water vapour) flow rate is generally from about 240 to about 1500 cm 3 /min, preferably from about 500 to about 1000 cm 3 /min.
- the reaction mixture which is utilized in the present invention also, includes a dopant material, in vapor phase, it positively affect the physical attributes of the titanium dioxide formed.
- the TiCl 4 reactant, water vapor and the dopant may be mixed in the reactor. It is preferred that the dopant vapor be introduced through the concentric inconel tube (c). Aliphatic alcohols, aromatic hydrocarbons and mixtures thereof can be used as dopants out of which ethanol is used for this present invention.
- Ti (OH) 4 ⁇ TiO 2 + 2H 2 O The size range of particles formed due to the above reactions can be controlled by reaction temperature and molar ratio of H 2 O/ TiCl 4 in the reactor. Separation of titanium dioxide particle from gas phase The TiO 2 particles formed are either amorphosuse or anatase and this powder is collected on a bag filter, made of Teflon which is aided by vacuum pump. The filter bag is maintained at temperatures in the range 130 to 140°C to avoid condensation.
- the titanium dioxide powder having amorphous phase resulting from gas phase hydrolysis of titanium chloride without dopant is calcined at a temperature in the range of 300 - 600°C and for a length of time in the range of 1 -4 hours to obtain rutile phase or mixtures there of with anatase phase.
- a vapor phase dopant such as ethanol
- the rutile formation temperature is reduced to as much as 150 - 400°C compared to other usual calcination treatments, and the calcination duration is also sufficiently shortened to limit the excessive particle growth through sintering.
- calcination temperature can range between 800°C to 1100°C in the gas phase hydrolysis for anatase to rutile transformation.
- calcinations temperature range can be reduced between 500 to 700°C.
- Example 1 illustrates the vapor phase hydrolysis of TiCi 4 and water without any dopant to synthesize titania nanopowders having the urtile phase.
- Example 2 illustrates the vapor phase hydrolysis of TiCl 4 and water with dopant as ethanol to synthesize titania nanopowders having the rutile phase.
- Example 1 Dry nitrogen (99.9%) is bubbled through a gas bottle containing titanium etrachloride (commercial grade) maintained at a temperature of 90°C and is directed through the central tube of the aerosol reactor. Concentration of TiCl 4 in the gas stream is determined by recording the weight of TiCl 4 before and after each experiment. A constant N 2 flow rate of 500 c Vmin through the TiCi 4 bubbler is used.
- the corresponding molar flow rate of TiCl 4 is 1.7 x 10 ⁇ 3 mol/min.
- Mass flow controllers (1259 B, MKS) precisely control all flows into reactor.
- the TiCl 4 vapor and the water vapor are mixed rapidly around the nozzle and form TiO 2 aerosol at near atmospheric pressure. Titanium dioxide particles produced by gas phase hydrolysis of TiCl 4 in the. aerosol reactor are collected in a bag filter made of Teflon.
- the titanium dioxide powder is obtained directly as dry powders for characterization.
- the exhoust gas is completely absorbed by a set of bubblers.
- Portions of the powders produced were heat treated in a conventional muffle furnace. Powder was calcined at 800°C for 3 firs. Rotameter is used for measuring the flow rate of air. TiO 2 is synthesized (without the use of dopants), in this example, the following range of reaction conditions is utilized.
- H 2 O / TiCl molar ration 15 Phase composition of collected particles was determined by X-ray diffraction (XRD) in a Philips Holland Exper-Pro diffractometer operating at 40kV, 20mA, using CuK ⁇ . Radiation.
- XRD X-ray diffraction
- Titanium dioxide powders synthesized at different molar ratios of TiCl 4 and water vapor in the reactor are given in Table 1 below.
- Table 2 shows the specific surface areas of the powders produced, as well as the rutile and anatase contents of those powders. Powders produced at the various molar ratios are designated as HI, H2, H3 and H4.
- Table 1 Aerosol Synthesis Condition of TiO 2 powder (Without gas phase dopant)
- Example 2 Using the reactor and the analytical methods of Example 1, doped titanium dioxide was prepared as follows. The dopant ethanol kept at room temperature (28°C) is introduced into the reactor through the third concentric tube. TiCl vapor, water vapor and ethanol are mixed rapidly around the nozzle and form TiO 2 aerosol at near atmospheric pressure. Ethanol molar concentration iii the range one to ten percent of the concentration of water vapor. Portions of the powders jproduced were heat treated in a conventional furnace. Powder was calcined at 500°C for 3 hrs. Titanium dioxide powders are synthesized at different molar ratios of H 2 O/TiCl 4 in the reactor is given in Table 3 below.
- Table 4 show the specific surface areas of the powders produced as well as the rutile and anatase contents of these powders. Powders produced at the various molar ratios are designated as EH1, EH2 EH3 and EH4. Table 3: Aerosol Synthesis Condition of Titanium Dioxide powder (with gas phase dopant)
- Table 5 illustrates the unique advantage of using dopant such as ethanol during the vapor phase hydrolysis step to achieve substantial reduction of the calcinations temperature required for obtaining titanium dioxide particles with rutile phase.
- dopant such as ethanol during the vapor phase hydrolysis step to achieve substantial reduction of the calcinations temperature required for obtaining titanium dioxide particles with rutile phase.
- Nano and sub micron size titanium dioxide particles having the rutile phase, anatase phase and mixtures there of could be synthesized at temperatures less than 400°C through vapor phase reaction with TiCl 4 as the precursor.
- the other reactant involved in the process is water and ethanol, which are of low cost and are environmentally green chemicals. 3.
- the process is less energy consuming that the other available process and involves negligible maintenance.
- Prior art processes such as the chloride process developed for rutile manufacture (by Dupont) involves oxidation of titanium tetra chloride at a temperature of 1000 - 1200°C.
- the high purity oxygen is obtained through cryogenic air separation and the reaction is highly exothermic leading to release of large amount of energy (-130.98KJ/mol at 1100°C) which is removed from the reactor through heat exchangers containing cooling water.
- the high energy consumption and wastage in this process is due to 1.
- the energy for cryogenic separation of air into high purity oxygen 2.
- Pre-heating of TiCl and oxygen to 1200°C. 3. Wastage of exothermic heat of reaction.
- the process of the present invention does not require pure oxygen and the maximum reaction temperature in the aerosol reactor can be controlled to about 150°C.
Abstract
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Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2003801109266A CN100532274C (en) | 2003-12-31 | 2003-12-31 | Synthesis of ultrafine rutile phase titanium dioxide particles at low temperature |
GB0614753A GB2427860B (en) | 2003-12-31 | 2003-12-31 | Synthesis of ultrafine rutile phase titanium dioxide particles at low temperature |
DE10394356.0T DE10394356B4 (en) | 2003-12-31 | 2003-12-31 | Synthesis of ultrafine titania particles in rutile phase at low temperature |
CA2551663A CA2551663C (en) | 2003-12-31 | 2003-12-31 | Synthesis of ultrafine rutile phase titanium dioxide particles at low temperature |
AU2003304660A AU2003304660B2 (en) | 2003-12-31 | 2003-12-31 | Synthesis of ultrafine rutile phase titanium dioxide particles at low temperature |
JP2005512731A JP4800768B2 (en) | 2003-12-31 | 2003-12-31 | Low temperature synthesis of ultrafine rutile phase titanium dioxide particles |
PCT/IN2003/000429 WO2005063629A1 (en) | 2003-12-31 | 2003-12-31 | Synthesis of ultrafine rutile phase titanium dioxide particles at low temperature |
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PCT/IN2003/000429 WO2005063629A1 (en) | 2003-12-31 | 2003-12-31 | Synthesis of ultrafine rutile phase titanium dioxide particles at low temperature |
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WO2005063629A1 true WO2005063629A1 (en) | 2005-07-14 |
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PCT/IN2003/000429 WO2005063629A1 (en) | 2003-12-31 | 2003-12-31 | Synthesis of ultrafine rutile phase titanium dioxide particles at low temperature |
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JP (1) | JP4800768B2 (en) |
CN (1) | CN100532274C (en) |
AU (1) | AU2003304660B2 (en) |
CA (1) | CA2551663C (en) |
DE (1) | DE10394356B4 (en) |
GB (1) | GB2427860B (en) |
WO (1) | WO2005063629A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006051061A1 (en) * | 2004-11-11 | 2006-05-18 | Basell Poliolefine Italia S.R.L. | Preparation of tio2 powders from a waste liquid containing titanium compounds |
US8564095B2 (en) | 2011-02-07 | 2013-10-22 | Micron Technology, Inc. | Capacitors including a rutile titanium dioxide material and semiconductor devices incorporating same |
US8609553B2 (en) | 2011-02-07 | 2013-12-17 | Micron Technology, Inc. | Methods of forming rutile titanium dioxide and associated methods of forming semiconductor structures |
CN117410365A (en) * | 2023-12-15 | 2024-01-16 | 宁波长阳科技股份有限公司 | Solar cell module reflective film and preparation method and application thereof |
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JP2008519750A (en) * | 2004-11-11 | 2008-06-12 | バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ | Production of TiO2 powder from waste liquid containing titanium compound |
EP1997781B1 (en) * | 2007-05-22 | 2014-07-16 | Evonik Degussa GmbH | Method for making titanium dioxide with variable sinter activity |
JP5578572B2 (en) * | 2011-04-29 | 2014-08-27 | 独立行政法人産業技術総合研究所 | Composite particles |
KR101290400B1 (en) | 2012-01-27 | 2013-07-26 | 군산대학교산학협력단 | Apparatus for preparing nano crystalline anatase titanium dioxide powder |
CN103693687B (en) * | 2013-12-09 | 2015-06-24 | 云南新立有色金属有限公司 | Method and system for preparing titanium dioxide |
KR101763357B1 (en) * | 2016-04-08 | 2017-08-01 | 케이씨 주식회사 | Preparation method of rutile titanium dioxide powder |
CN109126894B (en) * | 2018-08-04 | 2021-07-23 | 山东迅达化工集团有限公司 | Preparation method of titanium dioxide carrier |
CN109943103A (en) * | 2019-04-16 | 2019-06-28 | 正太新材料科技有限责任公司 | The preparation method and applications of rutile type titanium white |
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2003
- 2003-12-31 GB GB0614753A patent/GB2427860B/en not_active Expired - Fee Related
- 2003-12-31 JP JP2005512731A patent/JP4800768B2/en not_active Expired - Fee Related
- 2003-12-31 WO PCT/IN2003/000429 patent/WO2005063629A1/en active Application Filing
- 2003-12-31 DE DE10394356.0T patent/DE10394356B4/en not_active Expired - Fee Related
- 2003-12-31 AU AU2003304660A patent/AU2003304660B2/en not_active Ceased
- 2003-12-31 CN CNB2003801109266A patent/CN100532274C/en not_active Expired - Fee Related
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2006051061A1 (en) * | 2004-11-11 | 2006-05-18 | Basell Poliolefine Italia S.R.L. | Preparation of tio2 powders from a waste liquid containing titanium compounds |
US7780931B2 (en) | 2004-11-11 | 2010-08-24 | Basell Poliolefine Italia S.R.L. | Preparation for Tio2 powders from a waste liquid containing titanium compounds |
US8564095B2 (en) | 2011-02-07 | 2013-10-22 | Micron Technology, Inc. | Capacitors including a rutile titanium dioxide material and semiconductor devices incorporating same |
US8609553B2 (en) | 2011-02-07 | 2013-12-17 | Micron Technology, Inc. | Methods of forming rutile titanium dioxide and associated methods of forming semiconductor structures |
US8748283B2 (en) | 2011-02-07 | 2014-06-10 | Micron Technology, Inc. | Methods of forming capacitors and semiconductor devices including a rutile titanium dioxide material |
US8927441B2 (en) | 2011-02-07 | 2015-01-06 | Micron Technology, Inc. | Methods of forming rutile titanium dioxide |
US8936991B2 (en) | 2011-02-07 | 2015-01-20 | Micron Technology, Inc. | Methods of forming capacitors and semiconductor devices including a rutile titanium dioxide material |
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CN117410365A (en) * | 2023-12-15 | 2024-01-16 | 宁波长阳科技股份有限公司 | Solar cell module reflective film and preparation method and application thereof |
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DE10394356B4 (en) | 2014-04-10 |
JP2007527833A (en) | 2007-10-04 |
CA2551663A1 (en) | 2005-07-14 |
AU2003304660A1 (en) | 2005-07-21 |
AU2003304660B2 (en) | 2008-04-03 |
GB2427860B (en) | 2009-03-25 |
GB0614753D0 (en) | 2006-09-06 |
CN1886341A (en) | 2006-12-27 |
GB2427860A (en) | 2007-01-10 |
DE10394356T5 (en) | 2007-04-12 |
JP4800768B2 (en) | 2011-10-26 |
CA2551663C (en) | 2010-03-23 |
CN100532274C (en) | 2009-08-26 |
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