CN103709616A - Nanoscale halogen-free flame-retardant PBT composite material - Google Patents
Nanoscale halogen-free flame-retardant PBT composite material Download PDFInfo
- Publication number
- CN103709616A CN103709616A CN201210368748.8A CN201210368748A CN103709616A CN 103709616 A CN103709616 A CN 103709616A CN 201210368748 A CN201210368748 A CN 201210368748A CN 103709616 A CN103709616 A CN 103709616A
- Authority
- CN
- China
- Prior art keywords
- halogen
- nano
- pbt
- pbt composite
- antioxidant
- 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.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92723—Content, e.g. percentage of humidity, volatiles, contaminants or degassing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a nanoscale halogen-free flame-retardant PBT composite material. The nanoscale halogen-free flame-retardant PBT composite material comprises components by mass: 60%-75% of PBT, 5%-15% of nanoparticles, 18%-25% of a halogen-free flame retardant, 0.1%-0.3% of a surface treating agent, 0.2%-1.5% of a lubricant, 0.1%-1% of an antioxidant and 0-0.5% of a color material. The nanoscale halogen-free flame-retardant PBT composite material has the beneficial effects that by blending the nanoparticles with PBT and adding a proper amount of the halogen-free flame retardant, the surface treating agent and the like, not only can rigidity, heat resistance and stability of the material be greatly increased, but also effects of toughening and reinforcing and keeping relatively good strength can be achieved; the halogen-free flame retardant has smoke-suppressing, non-toxic and environment-friendly high flame-retardant performance; and the nanoscale halogen-free flame-retardant PBT composite material has excellent comprehensive performances, good processability and low cost.
Description
Technical field
The present invention relates to a kind of macromolecular material, specifically a kind of nano level halogen-free anti-flaming PBT composite.
Background technology
Polybutylene terephthalate (PBT) is one of five large-engineering plastics, is widely used in the industries such as electronics, electric, household electrical appliances.Yet pure PBT exists that notch impact toughness is low, fragility is large and the shortcoming such as poor fire, limits it in the application in some field.It is flame-retardant modified that prior art is used fire retardant to carry out PBT conventionally, although it is fine to apply at present the flame retardant effect of more halogenated flame retardant, in fire-retardant process, may produce two uh the toxicants such as English, furans, can not meet health, environmental requirement.
Summary of the invention
The object of the invention is to, a kind of good notch impact toughness, better mechanical strength and the good nano level halogen-free anti-flaming PBT composite of halogen-free flame-proof environmental protection condition are provided.
The technical solution adopted for the present invention to solve the technical problems is: nano level halogen-free anti-flaming PBT composite, its component by mass percent proportioning is: PBT 60%～75%, nanoparticle 5%～15%, halogen-free flame retardants 18%～25%, surface treatment agent 0.1%～0.3%, lubricant 0.2%～1.5%, oxidation inhibitor 0.1%～1%, colorant 0～0.5%.
Described PBT is polybutylene terephthalate, and limiting viscosity is 0.85～1.2dl/g.
Described nanoparticle is a kind of in nano silicon, nano-calcium carbonate, nanomete talc powder, nano diatomite, nano imvite, nano kaoline and nano-silicon nitride and silicon carbide compound, and the median size of this nanoparticle is between 10nm～100nm.
Described halogen-free flame retardants is organic phosphorus flame retardant, silicone flame retardant or nitrogenated flame retardant.
Described surface treatment agent is a kind of in lipid acid, calcium stearate, sodium stearate, Magnesium Stearate, Aluminate and alkyl hydrochlorate.
Described lubricant is one or more the mixture in polysiloxane, EVA wax, TAS-2A, ethylene bis stearic amide.
Described oxidation inhibitor is a kind of in compound, antioxidant 1010 or the antioxidant 1076 of antioxidant 1010, antioxidant 1076, antioxidant 1010 or antioxidant 1076 and irgasfos 168 and the compound of oxidation inhibitor JC-242.
The preparation method of above-mentioned nano level halogen-free anti-flaming PBT composite, comprises the following steps:
(1) after nanoparticle and surface treatment agent are taken by weight ratio, add in sonic oscillation producer or high-speed mixer, at 100 ℃～200 ℃ temperature, stir 20～60 minutes, make dispersedly, be then cooled to lower than 40 ℃ of dischargings, stand-by;
(2) PBT is dried to 3～5 hours at 130 ℃～140 ℃, moisture control is below 0.03%, stand-by;
(3) take by weight ratio PBT, halogen-free flame retardants, lubricant, oxidation inhibitor and the colorant after drying treatment, add high-speed mixer, the nanoparticle of processing through surface treatment agent of step (1) is added to high-speed mixer simultaneously, make fully to mix together 3～5 minutes;
(4) again the mixture of step (3) is dropped into twin screw extruder, control screw speed at 200～500 revs/min, barrel zone temperature, at 210 ℃～240 ℃, through twin screw extruder extruding pelletization, obtains nano level halogen-free anti-flaming PBT composite.
The invention has the beneficial effects as follows, by nanoparticle and PBT blend, and add appropriate halogen-free flame retardants, surface treatment agent etc., not only greatly improve rigidity, thermotolerance and the stability of material, can play effect toughness reinforcing, that strengthen and keep better intensity, and halogen-free flameproof have the high flame retardant usefulness that presses down cigarette, nontoxic, environmental protection, its high comprehensive performance, good processability, cost is low.
Embodiment
Below in conjunction with specific embodiment, further illustrate technical scheme of the present invention.
Embodiment 1:
A kind of nano level halogen-free anti-flaming PBT composite, its component by mass percent proportioning is: PBT 70%, nano silicon 10%, organic phosphorus flame retardant 18%, lipid acid 0.2%, polysiloxane 1%, antioxidant 1010 0.6%, colorant 0.2%, wherein, the limiting viscosity of PBT is 0.85～1.2dl/g, and the median size of nano silicon is between 10nm～100nm.
Preparation method: after (1) takes nano silicon and lipid acid by weight ratio, add in sonic oscillation producer or high-speed mixer, at 100 ℃～200 ℃ temperature, stir 20～60 minutes, make dispersed, then be cooled to lower than 40 ℃ of dischargings, stand-by; (2) PBT is dried to 3～5 hours at 130 ℃～140 ℃, moisture control is below 0.03%, stand-by; (3) take by weight ratio PBT, organic phosphorus flame retardant, polysiloxane, antioxidant 1010 and the colorant after drying treatment, add high-speed mixer, the nano silicon of simultaneously the process fatty acid treatment of step (1) being crossed adds high-speed mixer, makes fully to mix together 3～5 minutes; (4) again the mixture of step (3) is dropped into twin screw extruder, control screw speed at 200～500 revs/min, barrel zone temperature, at 210 ℃～240 ℃, through twin screw extruder extruding pelletization, obtains nano level halogen-free anti-flaming PBT composite.
Embodiment 2:
A kind of nano level halogen-free anti-flaming PBT composite, its component by mass percent proportioning is: the compound 0.9% of PBT 60%, nano-calcium carbonate 12%, organic phosphorus flame retardant 25%, calcium stearate 0.3%, TAS-2A 1.5%, antioxidant 1076 and irgasfos 168, colorant 0.3%, wherein, the limiting viscosity of PBT is 0.85～1.2dl/g, and the median size of nano-calcium carbonate is between 10nm～100nm.
Preparation method: after (1) takes nano-calcium carbonate and calcium stearate by weight ratio, add in sonic oscillation producer or high-speed mixer, at 100 ℃～200 ℃ temperature, stir 20～60 minutes, make dispersed, then be cooled to lower than 40 ℃ of dischargings, stand-by; (2) PBT is dried to 3～5 hours at 130 ℃～140 ℃, moisture control is below 0.03%, stand-by; (3) take by weight ratio compound and the colorant of PBT, organic phosphorus flame retardant, TAS-2A, antioxidant 1076 and irgasfos 168 after drying treatment, add high-speed mixer, the nano-calcium carbonate of processing through calcium stearate of step (1) is added to high-speed mixer simultaneously, make fully to mix together 3～5 minutes; (4) again the mixture of step (3) is dropped into twin screw extruder, control screw speed at 200～500 revs/min, barrel zone temperature, at 210 ℃～240 ℃, through twin screw extruder extruding pelletization, obtains nano level halogen-free anti-flaming PBT composite.
Embodiment 3:
A kind of nano level halogen-free anti-flaming PBT composite, its component by mass percent proportioning is: the compound 0.4% of PBT 75%, nano-silicon nitride and silicon carbide compound 5%, organic phosphorus flame retardant 18%, Magnesium Stearate 0.1%, ethylene bis stearic amide 1.5%, antioxidant 1076 and oxidation inhibitor JC-242, wherein, the limiting viscosity of PBT is 0.85～1.2dl/g, and the median size of nano-silicon nitride and silicon carbide compound is between 10nm～100nm.
Preparation method: after (1) takes nano-silicon nitride and silicon carbide compound and Magnesium Stearate by weight ratio, add in sonic oscillation producer or high-speed mixer, at 100 ℃～200 ℃ temperature, stir 20～60 minutes, make dispersed, then be cooled to lower than 40 ℃ of dischargings, stand-by; (2) PBT is dried to 3～5 hours at 130 ℃～140 ℃, moisture control is below 0.03%, stand-by; (3) take by weight ratio PBT, organic phosphorus flame retardant, ethylene bis stearic amide and antioxidant 1076 after drying treatment and the compound of oxidation inhibitor JC-242, add high-speed mixer, nano-silicon nitride and the silicon carbide compound through Magnesium Stearate, processed of step (1) are added to high-speed mixer simultaneously, make fully to mix together 3～5 minutes; (4) again the mixture of step (3) is dropped into twin screw extruder, control screw speed at 200～500 revs/min, barrel zone temperature, at 210 ℃～240 ℃, through twin screw extruder extruding pelletization, obtains nano level halogen-free anti-flaming PBT composite.
Claims (8)
1. a nano level halogen-free anti-flaming PBT composite, it is characterized in that, its component by mass percent proportioning is: PBT 60%～75%, nanoparticle 5%～15%, halogen-free flame retardants 18%～25%, surface treatment agent 0.1%～0.3%, lubricant 0.2%～1.5%, oxidation inhibitor 0.1%～1%, colorant 0～0.5%.
2. nano level halogen-free anti-flaming PBT composite according to claim 1, is characterized in that, described PBT is polybutylene terephthalate, and limiting viscosity is 0.85～1.2dl/g.
3. nano level halogen-free anti-flaming PBT composite according to claim 1, it is characterized in that, described nanoparticle is a kind of in nano silicon, nano-calcium carbonate, nanomete talc powder, nano diatomite, nano imvite, nano kaoline and nano-silicon nitride and silicon carbide compound, and the median size of this nanoparticle is between 10nm～100nm.
4. nano level halogen-free anti-flaming PBT composite according to claim 1, is characterized in that, described halogen-free flame retardants is organic phosphorus flame retardant, silicone flame retardant or nitrogenated flame retardant.
5. nano level halogen-free anti-flaming PBT composite according to claim 1, is characterized in that, described surface treatment agent is a kind of in lipid acid, calcium stearate, sodium stearate, Magnesium Stearate, Aluminate and alkyl hydrochlorate.
6. nano level halogen-free anti-flaming PBT composite according to claim 1, is characterized in that, described lubricant is one or more the mixture in polysiloxane, EVA wax, TAS-2A, ethylene bis stearic amide.
7. nano level halogen-free anti-flaming PBT composite according to claim 1, it is characterized in that, described oxidation inhibitor is a kind of in compound, antioxidant 1010 or the antioxidant 1076 of antioxidant 1010, antioxidant 1076, antioxidant 1010 or antioxidant 1076 and irgasfos 168 and the compound of oxidation inhibitor JC-242.
8. the preparation method of nano level halogen-free anti-flaming PBT composite according to claim 1, is characterized in that, comprises the following steps:
(1) after nanoparticle and surface treatment agent are taken by weight ratio, add in sonic oscillation producer or high-speed mixer, at 100 ℃～200 ℃ temperature, stir 20～60 minutes, make dispersedly, be then cooled to lower than 40 ℃ of dischargings, stand-by;
(2) PBT is dried to 3～5 hours at 130 ℃～140 ℃, moisture control is below 0.03%, stand-by;
(3) take by weight ratio PBT, halogen-free flame retardants, lubricant, oxidation inhibitor and the colorant after drying treatment, add high-speed mixer, the nanoparticle of processing through surface treatment agent of step (1) is added to high-speed mixer simultaneously, make fully to mix together 3～5 minutes;
(4) again the mixture of step (3) is dropped into twin screw extruder, control screw speed at 200～500 revs/min, barrel zone temperature, at 210 ℃～240 ℃, through twin screw extruder extruding pelletization, obtains nano level halogen-free anti-flaming PBT composite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210368748.8A CN103709616A (en) | 2012-09-28 | 2012-09-28 | Nanoscale halogen-free flame-retardant PBT composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210368748.8A CN103709616A (en) | 2012-09-28 | 2012-09-28 | Nanoscale halogen-free flame-retardant PBT composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103709616A true CN103709616A (en) | 2014-04-09 |
Family
ID=50402991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210368748.8A Pending CN103709616A (en) | 2012-09-28 | 2012-09-28 | Nanoscale halogen-free flame-retardant PBT composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103709616A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107254149A (en) * | 2017-07-06 | 2017-10-17 | 中山北化高分子材料有限公司 | Soft nanometer microcell toughened PET composite and preparation method thereof |
| CN107446324A (en) * | 2017-08-02 | 2017-12-08 | 广东锦湖日丽高分子材料有限公司 | A kind of inorganic nano-particle enhancing fire retardant PBT with no halogen material and preparation method thereof |
-
2012
- 2012-09-28 CN CN201210368748.8A patent/CN103709616A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107254149A (en) * | 2017-07-06 | 2017-10-17 | 中山北化高分子材料有限公司 | Soft nanometer microcell toughened PET composite and preparation method thereof |
| CN107446324A (en) * | 2017-08-02 | 2017-12-08 | 广东锦湖日丽高分子材料有限公司 | A kind of inorganic nano-particle enhancing fire retardant PBT with no halogen material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107286563B (en) | Intumescent flame retardant for ABS electrical switch outer cover and preparation and application thereof | |
| CN103554598B (en) | The preparation method of halogen-free flameproof high density polyethylene(HDPE)/ethylene-vinyl acetate copolymer | |
| CN112250985B (en) | Halogen-free flame-retardant ABS composition and preparation method and application thereof | |
| CN103709621A (en) | PBT environment-friendly and flame-retardant material toughened and reinforced by blending elastomer and micrometer particles | |
| Xia et al. | Cu2O based on core-shell nanostructure for enhancing the fire-resistance, antibacterial properties and mechanical properties of epoxy resin | |
| CN103849027A (en) | Nano polyethylene composite material and preparation method thereof | |
| CN103709616A (en) | Nanoscale halogen-free flame-retardant PBT composite material | |
| CN103881185A (en) | Fire-retardant modified polyethylene material and preparation method thereof | |
| CN103709663A (en) | Modified PET/PBT alloy material | |
| CN103709635A (en) | Glass fiber flame-retardant nanoparticle/PBT composite material | |
| CN103709631A (en) | Nanocomposite toughened and flame-retardant modified polybutylene terephthalate | |
| CN104419125A (en) | Flame-retardant toughening-modified PET/PBT blending alloy | |
| CN104672809A (en) | Toughened reinforced environment-friendly flame-retardant PBT/PET (polybutylene terephthalate/polyethylene terephthalate) alloy | |
| CN103881320A (en) | Nanometer flame-retardant polybutylene telephthalate material and preparation method thereof | |
| CN103613913A (en) | Halogen-free flame-retardant thermoplastic polyester elastomer material and preparation method thereof | |
| CN103102666A (en) | Flame retardant grade antibacterial office supply made of PC (polycarbonate)/ABS (acrylonitrile butadiene styrene) | |
| CN103102616A (en) | Flame retardant grade antibacterial office supply made of PVC (polyvinyl chloride)/ABS (acrylonitrile butadiene styrene) | |
| CN103709619A (en) | Glass fiber flame-retardant and micrometer calcium carbonate toughened and reinforced PBT composite material | |
| CN104829943A (en) | Fumed-silica-containing intumescent polypropylene flame retardant and preparation method of flame retardant | |
| CN103709589A (en) | Mica-ABS (Acrylonitrile Butadiene Styrene) flame-retardant insulation material and preparation method thereof | |
| CN104672811A (en) | Environment-friendly flame-retardant antistatic reinforced PBT/PET (polybutylene terephthalate/polyethylene terephthalate) composite material | |
| CN103709630A (en) | Nanoparticles and elastomer blended and halogen-free flame-retardant PBT composite material | |
| CN104419149A (en) | Carbon fiber reinforced and environment-friendly flame-retardant PBT(polybutylene terephthalate)/PET (polyethylene terephthalate) alloy | |
| CN104672812A (en) | Core-shell-structure-toughened halogen-free flame-retardancy-modified PET (polyethylene terephthalate) material | |
| CN104861616A (en) | Carbon nanofiber modified PC/PBT alloy and preparation method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140409 |