CN103144392A - Photostable antimicrobial polypropylene material product and preparation method thereof - Google Patents
Photostable antimicrobial polypropylene material product and preparation method thereof Download PDFInfo
- Publication number
- CN103144392A CN103144392A CN2013100631292A CN201310063129A CN103144392A CN 103144392 A CN103144392 A CN 103144392A CN 2013100631292 A CN2013100631292 A CN 2013100631292A CN 201310063129 A CN201310063129 A CN 201310063129A CN 103144392 A CN103144392 A CN 103144392A
- Authority
- CN
- China
- Prior art keywords
- polypropylene
- goods
- antioxidant
- nano
- modified material
- 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.)
- Granted
Links
Landscapes
- Physical Vapour Deposition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a photostable antimicrobial polypropylene material product and a preparation method thereof. A polypropylene material comprises nano titanium dioxide and nano silver, wherein a nano titanium dioxide film is coated on a formed product surface through a plasma sputtering technology. The modified polypropylene material product has a continuous antimicrobial effect, a crystal nucleation phenomenon of a nano material can be avoided, and the light stability is effectively increased.
Description
Technical field
The present invention relates to the polypropylene modified material of medical material or building materials field, especially a kind of light is stablized material modified goods of antibacterial polypropylene and preparation method thereof.
Background technology
Polypropylene has the advantages such as light specific gravity, cheap, good mechanical property and heat resistance be good with respect to general-purpose plastics, is usually used in the fields such as medical treatment, building materials as container, pipeline or other accessory.But little and this body structure of molecule due to polypropylene density, the easy breed bacteria of polypropylene material, thus health is produced harm.In addition, polypropylene the phenomenon of photostability inevitably can occur as a kind of resin material, thereby causes the aging of material, affects result of use and service life.
At present, someone studies inorganic antiseptic is added the effect that reaches antibiotic in polypropylene material, but, the inorganic antiseptic that this method adds mostly is silver-colored particle, exist difficulties in dispersion, the antibacterial effect performance is the shortcoming of (silver-series antibacterial agent performance effect needs more than 24 hours) slowly, and can't overcome equally the problem of above-mentioned photostability.
Summary of the invention
For overcoming above technological deficiency, the invention provides a kind of light and stablize material modified goods of antibacterial polypropylene and preparation method thereof.Comprise nano titanium oxide and Nano Silver in described polypropylene material, and form the nano titanium dioxide film layer at the product surface of moulding.
In order to reach above purpose, technical scheme of the present invention is: 1) adopt melt-mixing method, following compositions in weight percentage melt blending is made: polypropylene 85～92%, titanium dioxide nanoparticle 1～2%, nano-Ag particles 0.5～3%, anti-biotic material dispersed modifier 2～6%, antioxidant 0.01～2%, processing aid 0.01～8%; 2) the goods main body that is required form with above-mentioned intermingling material machine-shaping; 3) use plasma sputtering technique, take titanium as target, under the condition that oxygen exists, at the titanium deoxid film of surface sputtering one deck 100-500nm of said products main body thickness.
Preferably, described compositions in weight percentage is: polypropylene 88～90%, titanium dioxide nanoparticle 1.5～1.8%, nano-Ag particles 1～2%, anti-biotic material dispersed modifier 4～5%, antioxidant 0.1～1%, processing aid 0.1～5%.
Described polypropylene is isotactic polypropylene, it is characterized in that two defectives between structural chain have the average isotactic block length as assembly average greater than 70.Be preferably greater than 75, more preferably greater than 80, particularly preferably greater than 85 average isotactic block length.Most preferably greater than 90 average isotactic block length.
Described isotactic polypropylene weight average molecular weight (Mw) is 10000～700000g/mol, and preferred Mw is 20000～600000g/mol.
Described isotactic polypropylene number-average molecular weight (Mn) is 6000～400000g/mol, and preferred Mn is 10000～300000g/mol.
Described polyacrylic molecular weight distribution width (MWD) represents with the ratio of weight average molecular weight (Mw) and number-average molecular weight (Mn), the polypropylene that the preferred molecular weight dispersion of distribution is lower, and the scope of MWD is 2～5, preferred MWD scope is 2.5～4.
At least 163 ℃ of described polyacrylic fusing points, preferred more than 165 ℃.
The particle size range of described titanium dioxide nanoparticle between 50-100nm, preferred 70-90nm, preferred described titanium dioxide is the anatase titanium dioxide nano particle.
The particle size range of described nano-Ag particles between 10-50nm, preferred 25-35nm.
Described anti-biotic material dispersed modifier refers to that molecular weight is not high, can be to above-mentioned antimicrobial nano composition---nano titanium oxide and Nano Silver surface produce good wetting effect, thereby nano level antiseptic can evenly be distributed, the alkenes compounds that simultaneously has certain compatibility with polypropylene.The weight average molecular weight Mw of described anti-biotic material dispersed modifier is 3000～100000, and preferred Mw is 5000～50000 alkenes compounds.
The alkenes compounds of described anti-biotic material dispersed modifier is to contain ethene, propylene or alpha olefin oligomer, perhaps the oligomer of their composition, preferably propylene and alhpa olefin and composition, for example ethylene-propylene copolymer.
Described antioxidant refers to a kind of in phenolic antioxidant, phosphite ester kind antioxidant, sulfur-bearing class antioxidant, perhaps multiple composition wherein.Phenolic antioxidant such as BHT, 1010,1076 etc., phosphite ester kind antioxidant be as 168,626 etc., sulfur-bearing antioxidant such as PS802, DLTP, DLSP etc.
Described processing aid is one or more mixtures in stearic acid, stearate, White Mineral Oil, silicone oil or silicone, can improve processing characteristics in melting mixing or subsequent forming process.
In addition, as required, the present invention is not precluded within the usual auxiliaries of adding other macromolecular material on the basis of said components feature.
The preparation method that described light is stablized the material modified goods of antibacterial polypropylene is: 1) adopt the melt-blending process preparation, use banbury or Double-rotor continuous mixing equipment to realize mixing step, utilize single screw extrusion machine or double screw extruder to extrude, realize granulation step.Described melt-blending process refers to that in the temperature of processing temperature more than the polypropylene fusing point, 160～250 ℃ of processing temperatures, rotating speed 50～1200rpm mix various components by melting mixing equipment, and granulating and forming.Equipment comprises single screw extrusion machine, twin-screw extrusion, banbury, Double-rotor continuous mixing equipment, the preferred extruder of the present invention, more preferably double screw extruder; 2) adopt the forming polymer method, this area blow molding or injection molding process commonly used for example is prepared into above-mentioned raw materials the main body of the goods of required form; 3) use existing plasma coating machine, containing under the atmosphere of oxygen, use pure titanium to be target, carry out plasma sputtering technique, thereby the surface at said products forms titanium deoxid film, and wherein, the thickness of titanium deoxid film is 100-500nm, preferred 100-200nm, preferably, in described plasma sputtering technique, radio-frequency power is 40-150w, bias voltage 50-80V, sputtering time are 5-20 minute.
Described light is stablized the material modified goods of antibacterial polypropylene can be applied to field of medical materials, building materials field.Described goods can be container, pipeline, packaging cover, base etc., are not limited to of the present inventionly, and described goods can be the shapes such as tubbiness, ampuliform, tabular, tubulose, get final product so long as be suitable for the shape of machine-shaping.
The advantage of polypropylene modified material goods of the present invention is:
1) by add nano titanium oxide and nano-Ag particles in polypropylene material, make it possess continuous antibacterial effect, the mechanism of nanometer titanium dioxide antibiotic is photocatalysis, it can bring into play its antibacterial effect at once having under the environment of light, and nano-Ag particles wherein can continue its antibacterial effect of performance after 24 hours, therefore, can overcome the single defective of certain antiseptic on antibacterial effect and timeliness that add.
2) added the anti-biotic material dispersed modifier in polypropene composition of the present invention, it can make described nano level anti-biotic material evenly distribute in composition, thereby prevent the crystallization nucleation phenomenon of described nano material, guarantee the effective utilization to anti-biotic material.
3) by the plasma sputtering technology, obtain titanium deoxid film in the product surface sputter of making, described film even compact, with substrate in conjunction with effective, not only can reach antibiotic effect, can also stop that light contacts with the direct of described polypropylene product, improves its photostability.
The specific embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
Adopt melt-blending process by weight 85% PP, 2% titanium dioxide nanoparticle, 3% nano-Ag particles, 6% ethylene-propylene copolymer, 0.1% antioxidant BHT and 3.9% zinc stearate are mixed.
Said components is prepared polypropylene modified material with the twin-screw extrusion melting mixing.
Above-mentioned material adopts injection moulding machine to be injection molded into sheet material, place under field conditions (factors) and spend the night, then sheet material is placed under the atmosphere that contains oxygen, pure titanium is target, use existing plasma coating machine to carry out plasma sputtering technique, in described plasma sputtering technique, radio-frequency power is 40w, bias voltage 50V, sputtering time are 5 minutes.
After sputter, the titanium deoxid film thickness of plate surface is 100nm.
Embodiment 2
Adopt melt-blending process by weight 87% PP, 1% titanium dioxide nanoparticle, 1% nano-Ag particles, 6% alpha olefin oligomer, 0.1% irgasfos 168 and 4.9% silicone are mixed.
Said components is prepared polypropylene modified material with Double-rotor continuous mixing equipment melting mixing.
Above-mentioned material adopts blow molding machine to be blow molded into container, place under field conditions (factors) and spend the night, then container is placed under the atmosphere that contains oxygen, pure titanium is target, use existing plasma coating machine to carry out plasma sputtering technique, in described plasma sputtering technique, radio-frequency power is 100w, bias voltage 65V, sputtering time are 10 minutes.
After sputter, the titanium deoxid film thickness of plate surface is 325nm.
Embodiment 3
Adopt melt-blending process by weight 92% PP, 1% titanium dioxide nanoparticle, 0.5% nano-Ag particles, 4% ethylene-propylene copolymer, 1% antioxidant PS802 and 1.5% White Mineral Oil are mixed.
Said components is prepared polypropylene modified material with the banbury melting mixing.
Above-mentioned material adopts injection moulding machine to be injection molded into tubing, place under field conditions (factors) and spend the night, then tubing is placed under the atmosphere that contains oxygen, pure titanium is target, use existing plasma coating machine to carry out plasma sputtering technique, in described plasma sputtering technique, radio-frequency power is 150w, bias voltage 80V, sputtering time are 20 minutes.
After sputter, the titanium deoxid film thickness of plate surface is 500nm.
Comparative Examples 1
Adopt melt-blending process by weight 85% PP, 2% titanium dioxide nanoparticle, 3% nano-Ag particles, 0.1% antioxidant BHT and 9.9% zinc stearate are mixed.
Said components is adopted the method for embodiment 1, prepare polypropylene modified material with the twin-screw extrusion melting mixing, then, adopt injection moulding machine to be injection molded into sheet material, place under field conditions (factors) and spend the night.
Comparative Examples 2
Adopt melt-blending process by weight 87% PP, 2% nano-Ag particles, 6% alpha olefin oligomer, 0.1% irgasfos 168 and 4.9% silicone are mixed.
Said components is adopted the method for embodiment 2, prepare polypropylene modified material with Double-rotor continuous mixing equipment melting mixing, then, adopt blow molding machine to be blow molded into container, place under field conditions (factors) and spend the night.
To the final products of above-described embodiment 1-3 and Comparative Examples 1-2, carry out bacteriostasis rate, photostability and printing opacity observation experiment.
Experimental result such as table 1:
Table 1
test result shows, the time point of polypropylene modified material goods of the present invention 24 hours and 48 hours all reaches the bacteriostasis rate more than 99%, possesses simultaneously good photostability, and observe the crystallization nucleation phenomenon of not finding nano antibacterial agent through printing opacity, not only color and luster is inhomogeneous and do not adopt the sample (Comparative Examples 1) of anti-biotic material dispersed modifier, while is due to the crystallization nucleation phenomenon of antiseptic, affected bacteriostasis rate, in addition, the bacteriostasis rate of sample (Comparative Examples 2) within 24 hours that independent employing Nano Silver is antiseptic can't reach demand, bacteriostasis rate in 48 hours also has larger difference with product of the present invention, at last, do not use the sample (Comparative Examples 1 and 2) of titanium dioxide plasma sputtering plated film all to produce the crack in the photostability test, therefore obviously be inferior to product of the present invention on photostability.
Claims (10)
1. a light is stablized the material modified goods of antibacterial polypropylene, and the main component of described goods main body is for comprising by weight:
Polypropylene 85～92%;
Titanium dioxide nanoparticle 1～2%;
Nano-Ag particles 0.5～3%;
Anti-biotic material dispersed modifier 2～6%;
Antioxidant 0.01～2%;
Processing aid 0.01～8%;
And, the titanium oxide film layer that forms by the plasma sputtering technology is arranged on the surface of described goods.
2. a light is stablized the material modified goods of antibacterial polypropylene, and the main component of described goods main body is for comprising by weight:
Polypropylene 88～90%;
Titanium dioxide nanoparticle 1.5～1.8%;
Nano-Ag particles 1～2%;
Anti-biotic material dispersed modifier 4～5%;
Antioxidant 0.1～1%;
Processing aid 0.1～5%;
And, the titanium oxide film layer that forms by the plasma sputtering technology is arranged on the surface of described goods.
3. polypropylene modified material goods according to claim 1 and 2 is characterized in that:
Described polypropylene is isotactic polypropylene, and the defective between two structural chains of the isotactic polypropylene of telling has the average isotactic block length as assembly average greater than 70.
4. polypropylene modified material goods according to claim 1 and 2 is characterized in that:
The particle size range of described titanium dioxide nanoparticle is between 50-100nm.
5. polypropylene modified material goods according to claim 1 and 2 is characterized in that:
The particle size range of described nano-Ag particles is between 10-50nm.
6. polypropylene modified material goods according to claim 1 and 2 is characterized in that:
Described anti-biotic material dispersed modifier is the oligomer of ethene, propylene or alhpa olefin, perhaps the oligomer of their composition.
7. polypropylene modified material goods according to claim 1 and 2 is characterized in that:
Described antioxidant is a kind of in phenolic antioxidant, phosphite ester kind antioxidant, sulfur-bearing class antioxidant, perhaps multiple composition wherein, described phenolic antioxidant is selected from BHT, 1010 or 1076, described phosphite ester kind antioxidant is selected from 168 or 626, and described sulfur-bearing antioxidant is selected from PS802, DLTP or DLSP; Described processing aid is one or more mixtures in stearic acid, stearate, White Mineral Oil, silicone oil or silicone.
8. preparation method as the described polypropylene modified material goods of claim 1-7 any one is characterized in that comprising the following steps:
1) use the ratio of above-mentioned raw materials, adopt melt-blending process, prepare intermingling material;
2) adopt the forming polymer method, above-mentioned raw materials is prepared into the main body of the goods of required form;
3) containing under the atmosphere of oxygen, using pure titanium to be target, carrying out plasma sputtering technique, thereby forming titanium deoxid film on the surface of said products;
Wherein, melt-blending process refers to that in the temperature of processing temperature more than the polypropylene fusing point, 160～250 ℃ of processing temperatures, rotating speed 50～1200rpm mix various components by melting mixing equipment, and granulating and forming; The thickness of titanium deoxid film is 100-500nm.
9. the preparation method of polypropylene modified material goods claimed in claim 8 is characterized in that:
In described plasma sputtering technique, radio-frequency power is 40-150w, and bias voltage 50-80V, sputtering time are 5-20 minute.
10. application as the described polypropylene modified material goods of claim 1-7 any one is characterized in that:
Described polypropylene modified material product application is in medical material or building materials field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310063129.2A CN103144392B (en) | 2013-02-27 | 2013-02-27 | Photostable antimicrobial polypropylene material product and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310063129.2A CN103144392B (en) | 2013-02-27 | 2013-02-27 | Photostable antimicrobial polypropylene material product and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103144392A true CN103144392A (en) | 2013-06-12 |
| CN103144392B CN103144392B (en) | 2015-07-01 |
Family
ID=48542844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310063129.2A Expired - Fee Related CN103144392B (en) | 2013-02-27 | 2013-02-27 | Photostable antimicrobial polypropylene material product and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103144392B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524897A (en) * | 2013-10-09 | 2014-01-22 | 无锡会通新材料有限公司 | Environmental-friendly polypropylene foaming bead and preparation method thereof |
| WO2014048546A1 (en) * | 2012-09-28 | 2014-04-03 | Clariant International Ltd | Process for preparing a polypropylene-based object having an increased surface energy |
| CN110194889A (en) * | 2018-02-27 | 2019-09-03 | 嘉瑞塑胶科技有限公司 | A kind of method of the modified thermoplastic preparing antimicrobial attachment and product and the composition for being used to prepare modified thermoplastic |
| CN110983275A (en) * | 2019-12-25 | 2020-04-10 | 南京华塑增材制造有限公司 | Low-temperature preparation method of silver-doped titanium dioxide nano antibacterial composite coating on surface of PETG appliance |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060006382A1 (en) * | 2002-09-30 | 2006-01-12 | Incoat Gmbh | Composite material |
| CN101089038A (en) * | 2007-06-08 | 2007-12-19 | 深圳市科聚新材料有限公司 | Antibacterial polypropylene material and its prepn process |
| CN101255254A (en) * | 2008-03-28 | 2008-09-03 | 浙江高峰控股集团有限公司 | Antibacterial polypropylene pipes and antibacterial composite master batch as well as manufacturing method thereof |
| CN101377006A (en) * | 2007-08-29 | 2009-03-04 | 汉达精密电子(昆山)有限公司 | Method for preparing high catalytic activity titania thin film on plastic workpiece surface |
| CN201255254Y (en) * | 2008-08-28 | 2009-06-10 | 余锋 | Control valve of oxygenation pumping system |
| CN102336957A (en) * | 2010-07-29 | 2012-02-01 | 上海亿金纳米科技有限公司 | Method for preparing functional chips for manufacturing antibacterial fibers and plastics |
| CN102558676A (en) * | 2011-12-21 | 2012-07-11 | 上海普利特复合材料股份有限公司 | Highly-antibacterial polypropylene composite material and preparation method thereof |
-
2013
- 2013-02-27 CN CN201310063129.2A patent/CN103144392B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060006382A1 (en) * | 2002-09-30 | 2006-01-12 | Incoat Gmbh | Composite material |
| CN101089038A (en) * | 2007-06-08 | 2007-12-19 | 深圳市科聚新材料有限公司 | Antibacterial polypropylene material and its prepn process |
| CN101377006A (en) * | 2007-08-29 | 2009-03-04 | 汉达精密电子(昆山)有限公司 | Method for preparing high catalytic activity titania thin film on plastic workpiece surface |
| CN101255254A (en) * | 2008-03-28 | 2008-09-03 | 浙江高峰控股集团有限公司 | Antibacterial polypropylene pipes and antibacterial composite master batch as well as manufacturing method thereof |
| CN201255254Y (en) * | 2008-08-28 | 2009-06-10 | 余锋 | Control valve of oxygenation pumping system |
| CN102336957A (en) * | 2010-07-29 | 2012-02-01 | 上海亿金纳米科技有限公司 | Method for preparing functional chips for manufacturing antibacterial fibers and plastics |
| CN102558676A (en) * | 2011-12-21 | 2012-07-11 | 上海普利特复合材料股份有限公司 | Highly-antibacterial polypropylene composite material and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014048546A1 (en) * | 2012-09-28 | 2014-04-03 | Clariant International Ltd | Process for preparing a polypropylene-based object having an increased surface energy |
| CN103524897A (en) * | 2013-10-09 | 2014-01-22 | 无锡会通新材料有限公司 | Environmental-friendly polypropylene foaming bead and preparation method thereof |
| CN110194889A (en) * | 2018-02-27 | 2019-09-03 | 嘉瑞塑胶科技有限公司 | A kind of method of the modified thermoplastic preparing antimicrobial attachment and product and the composition for being used to prepare modified thermoplastic |
| CN110194889B (en) * | 2018-02-27 | 2022-11-15 | 嘉丰工业科技（惠州）有限公司 | Method for preparing modified thermoplastic plastic and product with microorganism adhesion resistance and composition for preparing modified thermoplastic plastic |
| CN110983275A (en) * | 2019-12-25 | 2020-04-10 | 南京华塑增材制造有限公司 | Low-temperature preparation method of silver-doped titanium dioxide nano antibacterial composite coating on surface of PETG appliance |
| CN110983275B (en) * | 2019-12-25 | 2022-02-01 | 南京华塑增材制造有限公司 | Low-temperature preparation method of silver-doped titanium dioxide nano antibacterial composite coating on surface of PETG appliance |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103144392B (en) | 2015-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103146119B (en) | A kind of wear-resistant antibacterial ABS is material modified and preparation method thereof | |
| CN105778435B (en) | PET compounds of heat-proof aging dielectric film and preparation method thereof | |
| TWI555765B (en) | Thermoplastics composition, polyethylene composition, polymeric article, and method of improving mechanical properties of thermoplastics | |
| CN103144392B (en) | Photostable antimicrobial polypropylene material product and preparation method thereof | |
| CN101759920A (en) | Polypropylene composite material with improved scraping and wiping resistance performance and preparation method thereof | |
| WO2022052408A1 (en) | Carbon nanotube master batch, and preparation method therefor and application thereof | |
| CN103205080B (en) | A kind of antibacterial Polystyrene material and preparation method thereof | |
| CN102181093A (en) | Anti-scratching polypropylene composite material and preparation method thereof | |
| CN103275370A (en) | Ultraviolet light shielding, anti-bacterial, antifouling multifunctional color master batch and preparation method thereof | |
| CN112920509A (en) | Antibacterial polypropylene composite material and preparation method thereof | |
| CN103601960B (en) | Polypropylene composite material, its preparation method and application | |
| Balamurugan et al. | Effects of nanotalc inclusion on mechanical, microstructural, melt shear rheological, and crystallization behavior of polyamide 6‐based binary and ternary nanocomposites | |
| CN114058115B (en) | Antibacterial and antiviral high-impact polypropylene composition and preparation method and application thereof | |
| CN109354773A (en) | The nucleating agent application tackiness in the precipitation for reducing PP composite material | |
| CN109627715A (en) | A kind of impact-resisting and heat resistant antibacterial polylactic acid composition and preparation method thereof | |
| Li et al. | Effect of malonic acid treatment on crystal structure, melting behavior, morphology, and mechanical properties of isotactic polypropylene/nano-CaCO3 composites | |
| Denac et al. | Polypropylene/talc/SEBS (SEBS-g-MA) composites. Part 1. Structure | |
| CN105623106B (en) | Rub resistance, the modified random copolymerization of resistance to scratch polypropylene material and preparation method thereof | |
| CN101691442A (en) | Heat-resistant resin composition and insulated wire insulated therewith | |
| CN112812432B (en) | Preparation method of polypropylene magnetic composite material | |
| CN103146168B (en) | Modified polycarbonate medical material and preparation method thereof | |
| Russo et al. | Thermo‐mechanical behavior of poly (butylene terephthalate)/silica nanocomposites | |
| CN1847299A (en) | Ultrahigh molecular weight polyethylene composition capable of being extrusion molded and its prepn process | |
| CN104861436A (en) | Nancomposite material of polytrimethylene terephthalate | |
| Garofalo et al. | Nanostructural modifications of polyamide/MMT hybrids under isothermal and nonisothermal elongational flow |
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 |
Granted publication date: 20150701 Termination date: 20190227 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |