CN105110334A - Preparation method for spherical silicon carbide - Google Patents
Preparation method for spherical silicon carbide Download PDFInfo
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- CN105110334A CN105110334A CN201510473646.6A CN201510473646A CN105110334A CN 105110334 A CN105110334 A CN 105110334A CN 201510473646 A CN201510473646 A CN 201510473646A CN 105110334 A CN105110334 A CN 105110334A
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Abstract
The invention discloses a preparation process for spherical silicon carbide. The preparation process aims to overcome the problem that in the prior art, the process is complex and the shape is difficult to control. The preparation method comprises the main steps: (1) mixing and stirring phenol, alkali and a formaldehyde solution, and after reaction, performing reduced pressure distillation to obtain a prepolymer; (2) stirring a macromolecular template with an acidic solution to obtain a clear solution and then adding TEOS and the prepolymer, transferring the solution to a culture dish after being stirred, and putting the culture dish in an oven to obtain a thin film material; and (III) grinding the thin film material and sieving, putting the ground thin film material in a vacuum tubular furnace, introducing argon into the furnace to roast the material to 800-1350 DEG C, and finally cooling the material to room temperature to obtain a spherical silicon carbide product which is placed in a glove box. The preparation method disclosed by the invention is simple in reaction process, it is easy to control shape and easy to operate.
Description
Technical field
The present invention relates to carbofrax material production technical field, particularly a kind of preparation technology of spherical carbide silicon, belongs to inorganic materials and prepares scope.
Background technology
Silicon carbide is a kind of semiconductor material, it has excellent physical and chemical performance, as: high physical strength, high temperature resistant, corrosion-resistant, thermal conductivity is good, has excellent Electronic Performance simultaneously, and, electronics, photoelectronics and biomedical sector micro-in mechanical industry have a wide range of applications.The strong replacer of silicon is considered to, in particular for high-voltage, superpower, high temperature and high-frequency element etc. at microelectronics industry silicon carbide.In addition, silicon carbide is also extensively used as the toughener of the matrix material such as pottery, metal.
Recent study shows that the electronic property of carbofrax material and its size and surface component are in close relations, and the silicon carbide isomr found at present is more than kind more than 250, and wherein the performance of silicon carbide nano material will far above common silicon carbide powder material.The method that tradition prepares silicon carbide nano material mainly contains the physical methods such as lf, arc-over and pulsed laser deposition, and carbothermic reduction, chemical vapour deposition, sol-gel method, SHS process and hydrothermal/solvent heat etc. chemical process.These class methods generally need be carried out at relatively high temperatures, bring certain difficulty to the pattern of target product and size regulation and control.
Current research is more for the report of silicon carbide nanometer line, nanometer rod.Mentioning one as Chinese patent (publication number: CN1762801A) utilizes sucrose or PEG to be carbon source, and positive silicon ester is the method for silicon source synthesizing silicon carbide nano wire; Chinese patent (publication number: CN1962433A) is for the method for silicon carbide nanometer line prepared by raw material with sucrose and silicon sol; Chinese patent (publication number: CN102432013) discloses a kind of report using water glass and starch or Sucrose synthesis nanometer silicon carbide.Shi Limin etc. mention and utilize that silica flour and resol are mixed at bag in (" silicate journal " 11 phases in 2006, P1397-1401), a kind of submicron silicon carbide powders of generation after carbonization and 1500 degree sintering, and this powder has globosity.Also do not prepare the report of spherical carbide silicon at present easily, the invention provides a kind of short-cut method preparing spherical carbide silicon.
Summary of the invention
The present invention will to solve in current silicon carbide preparation process that process is complicated, material purity requirement is high, material morphology is not easy the problems such as control.
The invention provides a kind of simple and convenient process for preparing of spherical carbide silicon, concrete technical scheme is as follows:
(1), by phenol, alkali and formaldehyde solution, in the ratio mix and blend certain hour of 1: 0.2: 0.5-1: 1: 1, are slowly warmed up to 45-100 degree reaction 1-5 hour, are cooled to reduced pressure at room temperature distillation and obtain performed polymer;
(2), high polymer templates and acid solution stirring are obtained settled solution, then TEOS and performed polymer (high polymer templates/acid/TEOS/ performed polymer ratio is 1: 0.1: 1: 1-1: 0.1: 5: 3) is added, stirring obtains homogeneous solution, move on in culture dish by this solution, being placed in baking oven spends the night obtains transparent orange yellow film material;
(3), step (two) complete after by thin-film material grind after sieve, sample thief is placed in the containing vacuum tube furnace being furnished with vacuum pump, first exhaust stove is vacuumized, pass into argon gas subsequently, keep flow velocity be 60-120 ml/min.350 degree are raised to, roasting 1-5 hour with the temperature rise rate of 1-5 degree/min; 800-1350 degree is raised to again, roasting 2-4 hour with the temperature rise rate of 1-5 degree/min; Finally obtain spherical carbide silicon product with the rate of cooling cool to room temperature of 1-5 degree/min, be placed in glove box.
The present invention first prepares performed polymer and then utilizes high polymer templates and acid solution to be introduced by TEOS, obtains the solution of homogeneous dispersion, is beneficial to next step like this and obtains homogeneous colloidal sol, to obtain the homogeneous distribution of carbon atom and Siliciumatom; Again finely dispersed for carbon silicon gel is carried out high temperature cabonization, first raise with temperature has the carbon ball of part to separate from homogeneous phase, and then silicon infiltration, in carbon ball, generates spherical carbofrax material at a proper temperature.
As preferably, described phenol, the ratio of alkali and formaldehyde solution is 1: 0.3: 1.
As preferably, in step (), temperature of reaction is 55-75 degree, and the reaction times is 1-3 hour.Such treatment effect is better.
As preferably, the high polymer templates described in step (two) is selected from F127 and P123, and acid is selected from one or more in strong phosphoric acid, concentrated hydrochloric acid, concentrated nitric acid, the vitriol oil.
As preferably, in step (two), high polymer templates/acid/TEOS/ performed polymer ratio is 1: 0.1: 2: 3.
As preferably, in step (three), the flow velocity of argon gas is 100-120 ml/min; 350 degree are raised to, roasting 3-4 hour with the temperature rise rate of 1-2 degree/min; 1100-1350 degree is raised to again, roasting 3-4 hour with the temperature rise rate of 3-5 degree/min; Last with 2-3 degree/min of cool to room temperature.Temperature rise rate, terminal temperature, soaking time are all prepare the important factor of spherical carbide silicon herein, and temperature controlled getting well just can obtain spherical carbide silicon.
The invention has the beneficial effects as follows:
(1), the spherical carbide silicon prepared of the present invention has good globosity, has higher stability;
(2), the inventive method prepares that the method for spherical carbide silicon is easy, step simple, processing ease.
Accompanying drawing explanation
Accompanying drawing 1 is the scanning electron microscope (SEM) photograph of embodiment three gained spherical carbide silicon.
Embodiment
Embodiment 1:
One, by 20 grams of phenol, the formalin mix and blend of 4.5 grams of sodium hydroxide and 34.5 grams of 37wt.% 10 minutes, is slowly warming up to 75 degree and reacts 1 hour, is cooled to reduced pressure at room temperature distillation and obtains performed polymer.
Two, by 50 grams of F127 and 32.5 grams of 0.1 mol/L dissolve with hydrochloric acid solution in 250 grams of ethanol, stir obtain settled solution, then add 68 grams of TEOS and 32.5 gram performed polymers, stir obtain homogeneous solution.Move on in culture dish by this solution, being placed in baking oven spends the night obtains transparent orange yellow film material.
Three, cross 200 mesh sieves by after thin-film material grinding, sample thief 10 grams, is placed in the containing vacuum tube furnace being furnished with vacuum pump, and first exhaust makes stove vacuumize in 10 minutes, passes into argon gas subsequently, keeps flow velocity to be 120 ml/min.350 degree are raised to, roasting 3 hours with the temperature rise rate of 1 degree/min; 800 degree are raised to again, roasting 2 hours with the temperature rise rate of 5 degrees/min; Finally obtain product with the rate of cooling cool to room temperature of 2 degrees/min, be placed in glove box, be designated as A.The concrete pattern of product is summarized in table one.
Embodiment 2:
One, by 20 grams of phenol, the formalin mix and blend of 4.5 grams of sodium hydroxide and 34.5 grams of 37wt.% 10 minutes, is slowly warming up to 75 degree and reacts 2 hours, is cooled to reduced pressure at room temperature distillation and obtains performed polymer.
Two, by 50 grams of F127 and 32.5 grams of 0.1 mol/L dissolve with hydrochloric acid solution in 250 grams of ethanol, stir obtain settled solution, then add 68 grams of TEOS and 32.5 gram performed polymers, stir obtain homogeneous solution.Move on in culture dish by this solution, being placed in baking oven spends the night obtains transparent orange yellow film material.
Three, cross 200 mesh sieves by after thin-film material grinding, sample thief 10 grams, is placed in the containing vacuum tube furnace being furnished with vacuum pump, and first exhaust makes stove vacuumize in 10 minutes, passes into argon gas subsequently, keeps flow velocity to be 100 ml/min.350 degree are raised to, roasting 3 hours with the temperature rise rate of 2 degrees/min; 1100 degree are raised to again, roasting 2 hours with the temperature rise rate of 5 degrees/min; Finally obtain product with the rate of cooling cool to room temperature of 2 degrees/min, be placed in glove box, be designated as B.The concrete pattern of product is summarized in table one.
Embodiment 3:
One, by 20 grams of phenol, 4.5 grams of sodium hydroxide, 10 grams of trioxymethylenes and 30 ml water mix and blends 10 minutes, be slowly warming up to 75 degree and react 1 hour, is cooled to reduced pressure at room temperature distillation and obtains performed polymer.
Two, by 52 grams of F127 and 32.5 grams of 0.2 mol/L dissolve with hydrochloric acid solution in 260 grams of ethanol, stir obtain settled solution, then add 68 grams of TEOS and 32.6 gram performed polymers, stir obtain homogeneous solution.Move on in culture dish by this solution, being placed in baking oven spends the night obtains transparent orange yellow film material.
Three, after grinding, 200 orders sieve, and sample thief 5 grams, is placed in the containing vacuum tube furnace being furnished with vacuum pump, and first exhaust makes stove vacuumize in 10 minutes, passes into argon gas subsequently, keeps flow velocity to be 120 ml/min.350 degree are raised to, roasting 3 hours with the temperature rise rate of 1 degree/min; 1300 degree are raised to again, roasting 2 hours with the temperature rise rate of 5 degrees/min; Last with the rate of cooling cool to room temperature of 2 degrees/min, obtain product, be placed in glove box, be designated as C.Concrete pattern is summarized in table one.
Embodiment 4:
One, by 10 grams of phenol, the formalin mix and blend of 3.5 grams of potassium hydroxide and 20 grams of 37wt.% 30 minutes, is slowly warming up to 75 degree and reacts 1 hour, be cooled to room temperature and obtain performed polymer.
Two, by 45 grams of P123 and 32.5 grams of 0.2 mol/L dissolve with hydrochloric acid solution in 300 grams of propyl alcohol, stir obtain settled solution, then add 80 grams of TEOS and 20 gram performed polymers, stir obtain homogeneous solution.Move on in culture dish by this solution, being placed in baking oven spends the night obtains transparent orange yellow film material.
Three, after grinding, 200 orders sieve, and sample thief 5 grams, is placed in the containing vacuum tube furnace being furnished with vacuum pump, and first exhaust makes stove vacuumize in 10 minutes, passes into argon gas subsequently, keeps flow velocity to be 120 ml/min.350 degree are raised to, roasting 3 hours with the temperature rise rate of 1 degree/min; 1200 degree are raised to again, roasting 2 hours with the temperature rise rate of 5 degrees/min; Last with the rate of cooling cool to room temperature of 3 degrees/min, obtain product, be placed in glove box, be designated as D.Concrete pattern is summarized in table one.
Embodiment 5:
One, by 20 grams of phenol, the formalin mix and blend of 4.5 grams of sodium hydroxide and 34.5 grams of 37wt.% 10 minutes, is slowly warming up to 100 degree and reacts 3 hours, is cooled to reduced pressure at room temperature distillation and obtains performed polymer.
Two, by 52 grams of F127 and 32.5 grams of 0.2 mol/L dissolve with hydrochloric acid solution in 200 grams of ethanol, stir obtain settled solution, then add 128 grams of TEOS and 32.6 gram performed polymers, stir obtain homogeneous solution.Move on in culture dish by this solution, being placed in baking oven spends the night obtains transparent orange yellow film material.
Three, after grinding, 200 orders sieve, and sample thief 10 grams, is placed in the containing vacuum tube furnace being furnished with vacuum pump, and first exhaust makes stove vacuumize in 10 minutes, passes into argon gas subsequently, keeps flow velocity to be 120 ml/min.350 degree are raised to, roasting 2 hours with the temperature rise rate of 2 degrees/min; 1350 degree are raised to again, roasting 2 hours with the temperature rise rate of 3 degrees/min; Last with the rate of cooling cool to room temperature of 2 degrees/min, obtain product, be placed in glove box, be designated as E.Concrete pattern is summarized in table one.
Comparative example 1:
One, by 20 grams of phenol, the formalin mix and blend of 4.5 grams of sodium hydroxide and 34.5 grams of 37wt.% 10 minutes, is slowly warming up to 45 degree and reacts 1 hour, is cooled to reduced pressure at room temperature distillation and obtains performed polymer.
Two, by 50 grams of F127 and 32.5 grams of 0.1 mol/L dissolve with hydrochloric acid solution in 250 grams of ethanol, stir obtain settled solution, then add 68 grams of TEOS and 32.5 gram performed polymers, stir obtain homogeneous solution.Move on in culture dish by this solution, being placed in baking oven spends the night obtains transparent orange yellow film material.
Three, cross 200 mesh sieves by after thin-film material grinding, sample thief 10 grams, is placed in the containing vacuum tube furnace being furnished with vacuum pump, and first exhaust makes stove vacuumize in 10 minutes, passes into argon gas subsequently, keeps flow velocity to be 100 ml/min.350 degree are raised to, roasting 3 hours with the temperature rise rate of 1 degree/min; 1300 degree are raised to again, roasting 2 hours with the temperature rise rate of 5 degrees/min; Finally obtain product with the rate of cooling cool to room temperature of 2 degrees/min, be placed in glove box, be designated as F.The concrete pattern of product is summarized in table one.
Comparative example 2:
One, by 20 grams of phenol, the formalin mix and blend of 4.5 grams of sodium hydroxide and 34.5 grams of 37wt.% 10 minutes, is slowly warming up to 75 degree and reacts 5 hours, is cooled to reduced pressure at room temperature distillation and obtains performed polymer.
Two, by 50 grams of F127 and 32.5 grams of 0.1 mol/L dissolve with hydrochloric acid solution in 250 grams of ethanol, stir obtain settled solution, then add 256 grams of TEOS and 32.5 gram performed polymers, stir obtain homogeneous solution.Move on in culture dish by this solution, being placed in baking oven spends the night obtains transparent orange yellow film material.
Three, cross 200 mesh sieves by after thin-film material grinding, sample thief 10 grams, is placed in the containing vacuum tube furnace being furnished with vacuum pump, and first exhaust makes stove vacuumize in 10 minutes, passes into argon gas subsequently, keeps flow velocity to be 120 ml/min.350 degree are raised to, roasting 3 hours with the temperature rise rate of 2 degrees/min; 1200 degree are raised to again, roasting 2 hours with the temperature rise rate of 5 degrees/min; Finally obtain product with the rate of cooling cool to room temperature of 2 degrees/min, be placed in glove box, be designated as G.The concrete pattern of product is summarized in table one.
Comparative example 3:
One, by 20 grams of phenol, the formalin mix and blend of 4.5 grams of sodium hydroxide and 34.5 grams of 37wt.% 10 minutes, is slowly warming up to 75 degree and reacts 2 hours, is cooled to reduced pressure at room temperature distillation and obtains performed polymer.
Two, by 50 grams of F127 and 32.5 grams of 0.1 mol/L dissolve with hydrochloric acid solution in 250 grams of ethanol, stir obtain settled solution, then add 68 grams of TEOS and 32.5 gram performed polymers, stir obtain homogeneous solution.Move on in culture dish by this solution, being placed in baking oven spends the night obtains transparent orange yellow film material.
Three, cross 200 mesh sieves by after thin-film material grinding, sample thief 15 grams, is placed in the containing vacuum tube furnace being furnished with vacuum pump, and first exhaust makes stove vacuumize in 10 minutes, passes into argon gas subsequently, keeps flow velocity to be 100 ml/min.350 degree are raised to, roasting 3 hours with the temperature rise rate of 2 degrees/min; 1500 degree are raised to again, roasting 2 hours with the temperature rise rate of 5 degrees/min; Finally obtain product with the rate of cooling cool to room temperature of 2 degrees/min, be placed in glove box, be designated as H.The concrete pattern of product is summarized in table one.
The physical parameter of the silicon carbide that table 1 the present invention prepares
| Product | Pattern |
| A | The mixture of amorphous carborundum and carbon |
| B | Spherical carbide silicon |
| C | Spherical carbide silicon |
| D | Spherical carbide silicon |
| E | Spherical carbide silicon |
| F | Amorphous products |
| G | Amorphous products |
| H | Spherically to break |
As shown in Table 1, this invention exploits a kind of method preparing spherical carbide silicon materials, but but cannot obtain globosity under the condition of comparative example.
Claims (6)
1. a simple and convenient process for preparing for spherical carbide silicon, is characterized in that: described preparation technology comprises the steps:
(1), by phenol, alkali and formaldehyde solution, in the ratio mix and blend certain hour of 1: 0.2: 0.5-1: 1: 1, are slowly warmed up to 45-100 degree reaction 1-5 hour, are cooled to reduced pressure at room temperature distillation and obtain performed polymer;
(2), high polymer templates and acid solution stirring are obtained settled solution, then TEOS and performed polymer (high polymer templates/acid/TEOS/ performed polymer ratio is 1: 0.1: 1: 1-1: 0.1: 5: 3) is added, stirring obtains homogeneous solution, move on in culture dish by this solution, being placed in baking oven spends the night obtains transparent orange yellow film material;
(3), step (two) complete after by thin-film material grind after sieve, sample thief is placed in the containing vacuum tube furnace being furnished with vacuum pump, first exhaust stove is vacuumized, pass into argon gas subsequently, keep flow velocity be 60-120 ml/min.350 degree are raised to, roasting 1-5 hour with the temperature rise rate of 1-5 degree/min; 800-1350 degree is raised to again, roasting 2-4 hour with the temperature rise rate of 1-5 degree/min; Finally obtain spherical carbide silicon product with the rate of cooling cool to room temperature of 1-5 degree/min, be placed in glove box.
2. the simple and convenient process for preparing of a kind of spherical carbide silicon according to claim 1, is characterized in that: described phenol, and the ratio of alkali and formaldehyde solution is 1: 0.3: 1.
3. the simple and convenient process for preparing of a kind of spherical carbide silicon according to claim 1, is characterized in that: in step (), temperature of reaction is 55-75 degree, and the reaction times is 1-3 hour.
4. the simple and convenient process for preparing of a kind of spherical carbide silicon according to claim 1, it is characterized in that: the high polymer templates described in step (two) is selected from F127 and P123, and acid is selected from one or more in strong phosphoric acid, concentrated hydrochloric acid, concentrated nitric acid, the vitriol oil.
5. the simple and convenient process for preparing of a kind of spherical carbide silicon according to claim 1, is characterized in that: in step (two), high polymer templates/acid/TEOS/ performed polymer ratio is 1: 0.1: 2: 3.
6. the simple and convenient process for preparing of a kind of spherical carbide silicon according to claim 1, is characterized in that: in step (three), the flow velocity of argon gas is 100-120 ml/min; 350 degree are raised to, roasting 3-4 hour with the temperature rise rate of 1-2 degree/min; 1100-1350 degree is raised to again, roasting 3-4 hour with the temperature rise rate of 3-5 degree/min; Last with 2-3 degree/min of cool to room temperature.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343065A (en) * | 2008-09-04 | 2009-01-14 | 复旦大学 | Nano-silicon dioxide hollow sphere material and method of preparing the same |
| CN102674354A (en) * | 2012-05-11 | 2012-09-19 | 南京工业大学 | Preparation method for mesoporous silicon carbide material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343065A (en) * | 2008-09-04 | 2009-01-14 | 复旦大学 | Nano-silicon dioxide hollow sphere material and method of preparing the same |
| CN102674354A (en) * | 2012-05-11 | 2012-09-19 | 南京工业大学 | Preparation method for mesoporous silicon carbide material |
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