CN103508475B - Preparation methods of alumina hollow microspheres - Google Patents
Preparation methods of alumina hollow microspheres Download PDFInfo
- Publication number
- CN103508475B CN103508475B CN201210203608.5A CN201210203608A CN103508475B CN 103508475 B CN103508475 B CN 103508475B CN 201210203608 A CN201210203608 A CN 201210203608A CN 103508475 B CN103508475 B CN 103508475B
- Authority
- CN
- China
- Prior art keywords
- microballoon
- aluminum
- urea formaldehyde
- preparation
- formaldehyde resins
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Catalysts (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to a preparation method of alumina hollow microspheres, aluminum nitrate is used as an aluminum source, urea formaldehyde resin microspheres are used as a template for adsorption of aluminum ions, under the effect of an epoxypropane ring opening reaction, a hydroxy coupling reaction and an oxygen coupling reaction of the aluminum ions absorbed on the urea formaldehyde resin microspheres are performed to obtain alumina gel microspheres, then the alumina gel microspheres are put in a polyethylene glycol aqueous solution for ultrasonic dispersion, and finally are baked to obtain the hollow alumina microspheres. Compared with the prior art, the preparation method adopts the urea formaldehyde resin as the template, the template is simple to prepare, the preparation method uses the effect of the epoxypropane ring opening reaction to perform the hydroxy coupling reaction and the oxygen coupling reaction of the aluminum ions perform to obtain the alumina gel microspheres, and the hollow alumina microspheres prepared by the preparation method are uniform in particle size and regular in shape.
Description
Technical field
The present invention relates to a kind of preparation method of aluminum oxide hollow microsphere, belong to the synthesis preparing technical field of compound.
Background technology
Aluminum oxide has the advantages such as high temperature resistant, corrosion-resistant and good insulating property, makes it obtain widespread use in fields such as catalysis industry, electronic industry, pottery, coating.Because its specific surface area is comparatively large, the advantages such as good stability, the application in absorption is also very extensive.But, aluminum oxide hollow microsphere except the advantage with aluminum oxide, because its hollow structure makes aluminum oxide hollow microsphere have larger pore volume.Therefore, it is in catalysis, and the effect of absorption aspect is more remarkable.
But the report at present for aluminum oxide hollow microsphere is very few.Chunhui Deng in 2011 etc. take glucose as the carbonaceous microballoon that carboxylate radical is rich in carbon source synthesis, then carbonaceous microballoon is put into ultrasonic 70min in the solution of aluminum nitrate, by product evaporate to dryness at 50 DEG C, vacuum after deionized water wash three times, calcine 1 hour at nitrogen environment 500 DEG C, then obtain aluminum oxide hollow microsphere.The diameter of gained aluminum oxide hollow microsphere is greatly about 500nm.This aluminum oxide hollow microsphere is quite obvious to the inrichment of phospho-peptide.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and provide a kind of uniform particle sizes, the preparation method of the aluminum oxide hollow microsphere that shape is regular.
Object of the present invention can be achieved through the following technical solutions:
A kind of preparation method of aluminum oxide hollow microsphere, take aluminum nitrate as aluminium source, utilize urea formaldehyde resins microballoon as template, Al adsorption ion, make to be adsorbed on the aluminum ion generation hydroxyl connection reaction on urea formaldehyde resins microballoon and the reaction of oxygen connection under the effect of propylene oxide ring-opening reaction, obtain alumina gel microballoon, then alumina gel microballoon is put into Aqueous Solutions of Polyethylene Glycol ultrasonic disperse, last roasting obtains hollow aluminium microballoon.
The method comprises the following steps:
(1) urea and formaldehyde are obtained by reacting urea formaldehyde resins precipitation in acidic aqueous solution, precipitate and dry to obtain urea formaldehyde resins microballoon with deionized water and washing with alcohol urea formaldehyde resins;
(2) nine water aluminum nitrates are dissolved in dehydrated alcohol the ethanolic soln obtaining aluminum nitrate;
(3) urea formaldehyde resins microballoon is rendered to absorption in the ethanolic soln of aluminum nitrate to soak, obtain being adsorbed with aluminum ions urea formaldehyde resins microballoon;
(4) aluminum ions urea formaldehyde resins microballoon will be adsorbed with and be placed in propylene oxide steam ambient 4 ~ 5 hours, and be adsorbed on the aluminum ion generation hydroxyl connection reaction on urea formaldehyde resins microballoon and the reaction of oxygen connection, obtain alumina gel microballoon;
(5) alumina gel microballoon is placed in Aqueous Solutions of Polyethylene Glycol ultrasonic disperse;
(6) filtration step (5) gains, by crossing, filtered product dries, roasting, obtains hollow aluminium microballoon.
Described aluminum oxide hollow microsphere diameter is 1 ~ 2 micron.
Urea described in step (1) and the mol ratio of formaldehyde are 1: 2.
Acidic aqueous solution described in step (1) is hydrochloric acid soln.
Nine water aluminum nitrates described in step (2) and the proportionlity of dehydrated alcohol are: dissolve nine water aluminum nitrate 0.3 ~ 0.5 gram in every milliliter of dehydrated alcohol.
The time needed for absorption immersion described in step (3) is 10 ~ 14 hours, and the temperature that absorption is soaked is 25 ~ 35 DEG C.
The massfraction of the Aqueous Solutions of Polyethylene Glycol described in step (5) is 4 ~ 6%.
The time of the ultrasonic disperse described in step (5) is 1 ~ 2 hour.
The temperature program(me) of the roasting described in step (6) is 30 DEG C and arrives 200 DEG C through 480min, and 200 DEG C keep 120min, arrive 350 DEG C through 120min, and 350 DEG C keep 60min, arrive 450 DEG C, then drop to room temperature through 120min.
Compared with prior art, the present invention has the following advantages:
A () the present invention adopts urea formaldehyde resins to be template, this Template preparation is easy;
B () the present invention utilizes the ring opening of propylene oxide that aluminum ion generation hydroxyl is joined and oxygen connection is obtained by reacting [Al (OH
2)
6]
3+mixture;
C aluminum oxide hollow microsphere uniform particle sizes prepared by () the present invention, shape is regular.
Accompanying drawing explanation
Fig. 1 is urea formaldehyde resins microballoon SEM photo;
Fig. 2 is aluminum oxide hollow microsphere SEM photo.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
In the beaker of the 100mL of 40mL distilled water, after adding the dissolving of 2.25g urea, then stir after respectively adding 6mL formaldehyde, finally add the hydrochloric acid of 0.2mL.Leave standstill and when solution reaction generates the state of cloud white, to continue reaction suction filtration after ten minutes, use a small amount of deionized water and ethanol to wash respectively and obtain urea formaldehyde resins precipitation for three times.Urea formaldehyde resins after separation to be deposited under room temperature dry 5 hours, and then 70 DEG C of dry 24h in an oven, and obtain urea formaldehyde resins microballoon, shape as shown in Figure 1.
Take 4g nine water aluminum nitrate and be placed in beaker containing 10ml dehydrated alcohol, magnetic agitation makes nine water aluminum nitrates dissolve completely.Prepared urea formaldehyde resins microballoon is put in the ethanolic soln of aluminum nitrate, absorption immersion 12 hours.Filtration gains are placed in propylene oxide steam ambient 4 hours by filtering mixt.Taking out renders in the Aqueous Solutions of Polyethylene Glycol of 5%, and ultrasonic disperse filtered after 1 hour.Dry in filtration product air at room temperature, finally calcine, during calcining, program temperature is 30 DEG C and arrives 200 DEG C through 480min, and 200 DEG C keep 120min, arrive 350 DEG C through 120min, and 350 DEG C keep 60min, 120min to arrive 450 DEG C, then drop to room temperature.Then aluminum oxide hollow microsphere is obtained as shown in Figure 2.
Embodiment 2
A kind of preparation method of aluminum oxide hollow microsphere, take aluminum nitrate as aluminium source, utilize urea formaldehyde resins microballoon as template, Al adsorption ion, make to be adsorbed on the aluminum ion generation hydroxyl connection reaction on urea formaldehyde resins microballoon and the reaction of oxygen connection under the effect of propylene oxide ring-opening reaction, obtain alumina gel microballoon, then alumina gel microballoon is put into Aqueous Solutions of Polyethylene Glycol ultrasonic disperse, last roasting obtains hollow aluminium microballoon.
The method comprises the following steps:
(1) urea and formaldehyde with mol ratio be 1: 2 ratio in acidic aqueous solution (hydrochloric acid soln), be obtained by reacting urea formaldehyde resins precipitation, precipitate with deionized water and washing with alcohol urea formaldehyde resins and dry and obtain urea formaldehyde resins microballoon;
(2) with the ratio of dissolving nine water aluminum nitrate 0.4 gram in every milliliter of dehydrated alcohol, nine water aluminum nitrates are dissolved in dehydrated alcohol the ethanolic soln obtaining aluminum nitrate;
(3) urea formaldehyde resins microballoon is rendered to absorption in the ethanolic soln of aluminum nitrate to soak, absorption soak time is 12 hours, and absorption soaking temperature is 30 DEG C, obtains being adsorbed with aluminum ions urea formaldehyde resins microballoon;
(4) aluminum ions urea formaldehyde resins microballoon will be adsorbed with and be placed in propylene oxide steam ambient 4 hours, and be adsorbed on the aluminum ion generation hydroxyl connection reaction on urea formaldehyde resins microballoon and the reaction of oxygen connection, obtain alumina gel microballoon;
(5) alumina gel microballoon is placed in the Aqueous Solutions of Polyethylene Glycol ultrasonic disperse 1 hour that massfraction is 5%;
(6) filtration step (5) gains, by crossing, filtered product dries, roasting, temperature program(me) during roasting is 30 DEG C and arrives 200 DEG C through 480min, 200 DEG C keep 120min, arrive 350 DEG C through 120min, 350 DEG C keep 60min, arrive 450 DEG C through 120min, then drop to room temperature, obtain hollow aluminium microballoon.
Obtained aluminum oxide hollow microsphere diameter is 1 ~ 2 micron.
Embodiment 3
A kind of preparation method of aluminum oxide hollow microsphere, take aluminum nitrate as aluminium source, utilize urea formaldehyde resins microballoon as template, Al adsorption ion, make to be adsorbed on the aluminum ion generation hydroxyl connection reaction on urea formaldehyde resins microballoon and the reaction of oxygen connection under the effect of propylene oxide ring-opening reaction, obtain alumina gel microballoon, then alumina gel microballoon is put into Aqueous Solutions of Polyethylene Glycol ultrasonic disperse, last roasting obtains hollow aluminium microballoon.
The method comprises the following steps:
(1) urea and formaldehyde with mol ratio be 1: 2 ratio in acidic aqueous solution (hydrochloric acid soln), be obtained by reacting urea formaldehyde resins precipitation, precipitate with deionized water and washing with alcohol urea formaldehyde resins and dry and obtain urea formaldehyde resins microballoon;
(2) with the ratio of dissolving nine water aluminum nitrate 0.3 gram in every milliliter of dehydrated alcohol, nine water aluminum nitrates are dissolved in dehydrated alcohol the ethanolic soln obtaining aluminum nitrate;
(3) urea formaldehyde resins microballoon is rendered to absorption in the ethanolic soln of aluminum nitrate to soak, absorption soak time is 10 hours, and absorption soaking temperature is 25 DEG C, obtains being adsorbed with aluminum ions urea formaldehyde resins microballoon;
(4) aluminum ions urea formaldehyde resins microballoon will be adsorbed with and be placed in propylene oxide steam ambient 4.5 hours, and be adsorbed on the aluminum ion generation hydroxyl connection reaction on urea formaldehyde resins microballoon and the reaction of oxygen connection, obtain alumina gel microballoon;
(5) alumina gel microballoon is placed in the Aqueous Solutions of Polyethylene Glycol ultrasonic disperse 1.5 hours that massfraction is 4%;
(6) filtration step (5) gains, by crossing, filtered product dries, roasting, temperature program(me) during roasting is 30 DEG C and arrives 200 DEG C through 480min, 200 DEG C keep 120min, arrive 350 DEG C through 120min, 350 DEG C keep 60min, arrive 450 DEG C through 120min, then drop to room temperature, obtain hollow aluminium microballoon.
Obtained aluminum oxide hollow microsphere diameter is 1 ~ 2 micron.
Embodiment 4
A kind of preparation method of aluminum oxide hollow microsphere, take aluminum nitrate as aluminium source, utilize urea formaldehyde resins microballoon as template, Al adsorption ion, make to be adsorbed on the aluminum ion generation hydroxyl connection reaction on urea formaldehyde resins microballoon and the reaction of oxygen connection under the effect of propylene oxide ring-opening reaction, obtain alumina gel microballoon, then alumina gel microballoon is put into Aqueous Solutions of Polyethylene Glycol ultrasonic disperse, last roasting obtains hollow aluminium microballoon.
The method comprises the following steps:
(1) urea and formaldehyde with mol ratio be 1: 2 ratio in acidic aqueous solution (hydrochloric acid soln), be obtained by reacting urea formaldehyde resins precipitation, precipitate with deionized water and washing with alcohol urea formaldehyde resins and dry and obtain urea formaldehyde resins microballoon;
(2) with the ratio of dissolving nine water aluminum nitrate 0.5 gram in every milliliter of dehydrated alcohol, nine water aluminum nitrates are dissolved in dehydrated alcohol the ethanolic soln obtaining aluminum nitrate;
(3) urea formaldehyde resins microballoon is rendered to absorption in the ethanolic soln of aluminum nitrate to soak, absorption soak time is 14 hours, and absorption soaking temperature is 35 DEG C, obtains being adsorbed with aluminum ions urea formaldehyde resins microballoon;
(4) aluminum ions urea formaldehyde resins microballoon will be adsorbed with and be placed in propylene oxide steam ambient 5 hours, and be adsorbed on the aluminum ion generation hydroxyl connection reaction on urea formaldehyde resins microballoon and the reaction of oxygen connection, obtain alumina gel microballoon;
(5) alumina gel microballoon is placed in the Aqueous Solutions of Polyethylene Glycol ultrasonic disperse 2 hours that massfraction is 6%;
(6) filtration step (5) gains, by crossing, filtered product dries, roasting, temperature program(me) during roasting is 30 DEG C and arrives 200 DEG C through 480min, 200 DEG C keep 120min, arrive 350 DEG C through 120min, 350 DEG C keep 60min, arrive 450 DEG C through 120min, then drop to room temperature, obtain hollow aluminium microballoon.
Obtained aluminum oxide hollow microsphere diameter is 1 ~ 2 micron.
Claims (9)
1. the preparation method of an aluminum oxide hollow microsphere, it is characterized in that, take aluminum nitrate as aluminium source, utilize urea formaldehyde resins microballoon as template, Al adsorption ion, makes to be adsorbed on the aluminum ion generation hydroxyl connection reaction on urea formaldehyde resins microballoon and the reaction of oxygen connection, obtains alumina gel microballoon under the effect of propylene oxide ring-opening reaction, then alumina gel microballoon is put into Aqueous Solutions of Polyethylene Glycol ultrasonic disperse, last roasting obtains hollow aluminium microballoon;
The method comprises the following steps:
(1) urea and formaldehyde are obtained by reacting urea formaldehyde resins precipitation in acidic aqueous solution, precipitate and dry to obtain urea formaldehyde resins microballoon with deionized water and washing with alcohol urea formaldehyde resins;
(2) nine water aluminum nitrates are dissolved in dehydrated alcohol the ethanolic soln obtaining aluminum nitrate;
(3) urea formaldehyde resins microballoon is rendered to absorption in the ethanolic soln of aluminum nitrate to soak, obtain being adsorbed with aluminum ions urea formaldehyde resins microballoon;
(4) aluminum ions urea formaldehyde resins microballoon will be adsorbed with and be placed in propylene oxide steam ambient 4 ~ 5 hours, and be adsorbed on the aluminum ion generation hydroxyl connection reaction on urea formaldehyde resins microballoon and the reaction of oxygen connection, obtain alumina gel microballoon;
(5) alumina gel microballoon is placed in Aqueous Solutions of Polyethylene Glycol ultrasonic disperse;
(6) filtration step (5) gains, by crossing, filtered product dries, roasting, obtains hollow aluminium microballoon.
2. the preparation method of a kind of aluminum oxide hollow microsphere according to claim 1, is characterized in that, described aluminum oxide hollow microsphere diameter is 1 ~ 2 micron.
3. the preparation method of a kind of aluminum oxide hollow microsphere according to claim 1, is characterized in that, the urea described in step (1) and the mol ratio of formaldehyde are 1:2.
4. the preparation method of a kind of aluminum oxide hollow microsphere according to claim 1, is characterized in that, the acidic aqueous solution described in step (1) is hydrochloric acid soln.
5. the preparation method of a kind of aluminum oxide hollow microsphere according to claim 1, is characterized in that, nine water aluminum nitrates described in step (2) and the proportionlity of dehydrated alcohol are: dissolve nine water aluminum nitrate 0.3 ~ 0.5 gram in every milliliter of dehydrated alcohol.
6. the preparation method of a kind of aluminum oxide hollow microsphere according to claim 1, is characterized in that, the time needed for absorption immersion described in step (3) is 10 ~ 14 hours, and the temperature that absorption is soaked is 25 ~ 35 DEG C.
7. the preparation method of a kind of aluminum oxide hollow microsphere according to claim 1, is characterized in that, the massfraction of the Aqueous Solutions of Polyethylene Glycol described in step (5) is 4 ~ 6%.
8. the preparation method of a kind of aluminum oxide hollow microsphere according to claim 1, is characterized in that, the time of the ultrasonic disperse described in step (5) is 1 ~ 2 hour.
9. the preparation method of a kind of aluminum oxide hollow microsphere according to claim 1, it is characterized in that, the temperature program(me) of the roasting described in step (6) is 30 DEG C and arrives 200 DEG C through 480min, 200 DEG C keep 120min, 350 DEG C are arrived through 120min, 350 DEG C keep 60min, arrive 450 DEG C, then drop to room temperature through 120min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210203608.5A CN103508475B (en) | 2012-06-19 | 2012-06-19 | Preparation methods of alumina hollow microspheres |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210203608.5A CN103508475B (en) | 2012-06-19 | 2012-06-19 | Preparation methods of alumina hollow microspheres |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103508475A CN103508475A (en) | 2014-01-15 |
| CN103508475B true CN103508475B (en) | 2015-06-03 |
Family
ID=49891972
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210203608.5A Expired - Fee Related CN103508475B (en) | 2012-06-19 | 2012-06-19 | Preparation methods of alumina hollow microspheres |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103508475B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108217703A (en) * | 2018-01-28 | 2018-06-29 | 蒋黎婷 | A kind of preparation method of hollow type aluminum oxide micro-sphere |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106673033B (en) * | 2015-11-11 | 2018-01-16 | 中国石油化工股份有限公司 | A kind of aluminum oxide micro-sphere of core shell structure and preparation method thereof |
| CN106350899B (en) * | 2016-08-24 | 2019-01-11 | 南京理工大学 | A kind of preparation method of hollow aluminum fiber |
-
2012
- 2012-06-19 CN CN201210203608.5A patent/CN103508475B/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| 以无机铝盐为前驱体用溶胶凝胶法合成中孔氧化铝;郝志显等;《物理化学学报》;20070331;第290页第1.2节制备过程部分以及第293页右栏倒数第2段 * |
| 尿素甲醛聚合反应中的沉淀现象;郝志显等;《化学学报》;20091231;第576页第1.2节制备部分 * |
| 新型氧化铝空心球的制备及表征;庞利萍等;《物理化学学报》;20080630;第1116页第1节实验部分 * |
| 表面活性剂存在条件下脲醛树脂微球的合成过程;郝志显等;《化学学报》;20120214;第331-338页 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108217703A (en) * | 2018-01-28 | 2018-06-29 | 蒋黎婷 | A kind of preparation method of hollow type aluminum oxide micro-sphere |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103508475A (en) | 2014-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103706342B (en) | Amino hybrid SiO 2aerogel material and application thereof | |
| CN102614819B (en) | Method for preparing magnetic mesoporous carbon nanometer microspheres with high adsorption property | |
| CN101264922B (en) | Method for preparing cerium oxide rhombus nano sheet-shaped material | |
| CN106622206B (en) | A kind of mesoporous ceria hollow sphere or mesoporous ceria/carbon composite hollow sphere and preparation method thereof | |
| CN102050479B (en) | Ceric oxide nanorod and preparation method thereof | |
| CN104307519B (en) | Gold supported strontium titanate catalyst for directly preparing hydrogen from formaldehyde aqueous solution and preparation method of gold supported strontium titanate catalyst for directly preparing hydrogen from formaldehyde aqueous solution | |
| CN103531365B (en) | The preparation method of electrode material for super capacitor cobalt-nickel oxide composite material | |
| CN103508475B (en) | Preparation methods of alumina hollow microspheres | |
| CN100551522C (en) | The method of producing interpose porus titanium dioxide photocatalyst by hydro-thermal method in weak acid condition | |
| CN104888710A (en) | Zeolite imidazole-like skeleton-mesoporous silica composite material and preparation methods thereof | |
| CN101264892A (en) | Method for preparing double-channel mesoporous silicon oxide hollow sphere | |
| CN108380197B (en) | Microwave activation based core-shell catalyst for preparing synthesis gas by reforming methane CO2 and preparation method thereof | |
| CN105642275A (en) | CeO2/Bi2WO6/MgAl-LDH composite photo-catalyst and preparation method and application thereof | |
| CN103642062B (en) | A kind of preparation method of high catalytic activity Red copper oxide/regenerated cellulose laminated film | |
| CN101723333A (en) | Method for preparing mesoporous metallic oxides with different appearances | |
| CN103127957A (en) | Mesoporous PW/MoO3-TiO2-SiO2 catalyst and preparation method and application thereof | |
| CN105126923A (en) | Sliver-titanium composite film loaded wood base material capable of degrading formaldehyde under visible light irradiation, and preparation method of sliver-titanium composite film loaded wood base material | |
| CN114558549B (en) | Use of carboxylate compounds as absorbents for capturing carbon dioxide | |
| CN103586054A (en) | Silica-supported lithium phosphate catalyst in eggshell shape, and preparation method and application thereof | |
| CN111266111B (en) | Nickel-doped titanium-oxygen cluster nano catalytic material, preparation method and application | |
| CN104386742A (en) | Mesoporous titanium dioxide having high crystallinity and large specific surface area and preparation method thereof | |
| CN103816924B (en) | A kind of preparation method of sulfur doping ceria meso-porous hollow ball photocatalyst | |
| CN110508260A (en) | A kind of preparation method of lead ion trace composite hollow microballoon | |
| CN103801328B (en) | The tai-gas clean-up catalyst of the soft carrier matrix of a kind of wire | |
| CN103435325B (en) | Preparation method for calcium-based aerogel material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150603 Termination date: 20180619 |