CN104591287A - Preparation method of nano zinc tungstate powder with antimicrobial property superior to silver tungstate - Google Patents

Preparation method of nano zinc tungstate powder with antimicrobial property superior to silver tungstate Download PDF

Info

Publication number
CN104591287A
CN104591287A CN201410827894.1A CN201410827894A CN104591287A CN 104591287 A CN104591287 A CN 104591287A CN 201410827894 A CN201410827894 A CN 201410827894A CN 104591287 A CN104591287 A CN 104591287A
Authority
CN
China
Prior art keywords
powder
antimicrobial
tungstate
zinc tungstate
silver
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
Application number
CN201410827894.1A
Other languages
Chinese (zh)
Other versions
CN104591287B (en
Inventor
王黔平
张家生
吴卫华
丁艳晓
李亚君
曹健
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hebei United University
Original Assignee
Hebei United University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hebei United University filed Critical Hebei United University
Priority to CN201410827894.1A priority Critical patent/CN104591287B/en
Publication of CN104591287A publication Critical patent/CN104591287A/en
Application granted granted Critical
Publication of CN104591287B publication Critical patent/CN104591287B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Abstract

The invention discloses a preparation method of nano zinc tungstate powder with antimicrobial property superior to silver tungstate. Zinc tungstate serves as a multifunctional material and attains wide attention because of excellent electric, optic, magnetic properties. The nano zinc tungstate antimicrobial powder is prepared by an ultrasonic chemical precipitation method which is simple in preparation process, low in reaction temperature and short in time; the antimicrobial effect of the nano zinc tungstate antimicrobial powder is compared with that of silver tungstate powder which is synthesized under the same condition. The preparation method of the nano zinc tungstate powder is characterized by taking Na2WO4 and Zn(NO3)2 as raw materials for preparing a mixed solution with a certain concentration, reacting at the temperature of 30-60 DEG C for 10-50 minutes under the ultrasonic condition and finally preparing white amorphous zinc tungstate antimicrobial powder with diameter of about 70nm and uniformly-distributed particles; in the test taking staphylococcus aureus as a strain, the change of the diameter of an antimicrobial ring of the zinc tungstate antimicrobial powder shows that the antimicrobial effect is superior to that of the silver tungstate antimicrobial powder under the same process condition. The nano zinc tungstate powder takes an active role in antimicrobial paper and antimicrobial plastic products.

Description

A kind of anti-microbial property is better than the nanometer zinc tungstate raw powder's production technology of wolframic acid silver
Technical field
The invention belongs to the technology of preparing of powder, is the nanometer zinc tungstate raw powder's production technology that a kind of anti-microbial property is better than wolframic acid silver, relates to the method adopting sonochemistry precipitator method synthesis of nano zinc tungstate antimicrobial powder.
Background technology
Silver system anti-biotic material has become most widely used a kind of antiseptic-germicide because having the advantage such as antibacterial wide spectrum, heat-resisting, the good endurance of safety, and traditional idea thinks that silver material will have larger advantage than non-silver material at antibiosis.But the wolframic acid prepared under true rare research same process condition silver is compared with zinc tungstate, to the antibacterial effect of streptococcus aureus how.The present invention adopts the nanometer zinc tungstate inorganic antibiosis powder of ultrasound synthesis for white, within the specific limits, all has larger advantage than the band color wolframic acid aluminium powder synthesized under same condition from anti-microbial property to color aspect.Experiment shows, compared with the wolframic acid aluminium powder prepared with ultrasonic method, the antibacterial effect of nanometer zinc tungstate powder prepared by ultrasonic method significantly improves.Reason may be that the metamict crystals structure of zinc tungstate makes its activity comparatively large, is easier to stripping Zn 2+caused by ion.
Zinc tungstate is a kind of broad-spectrum functional materials, have the character such as superior electricity, optics, magnetics to receive pay close attention to widely because of it, its micro Nano material has larger application prospect in luminescent material, catalytic material, magnetic material, laser donor material, anti-biotic material etc.The method preparing tungstate has a lot, the present invention explores the preparation for the superfine zinc tungstate antimicrobial powder of excellent antibacterial performance of building-up process is simple, temperature of reaction is low, the time the is short sonochemistry precipitator method, and compares with the silver tungstate antibacterial effect of synthesizing under same condition.
Wolframite structure is belonged to according to bibliographical information zinc tungstate.The chemical composition of wolframite is (Fe, Mn, Zn, Mg, Ca, Cu) WO 4, crystal belongs to monoclinic oxide mineral.
Zinc tungstate structure formation is ABO 4type, wherein A is Zn 2+ion; , B is W 4+ion; O is O 2-ion.In its structure, oxygen makes approximate hexagonal closest packing in parallel (100) direction, A, B two portions positively charged ion alternate ordered distribution between the octahedral layer in parallel (100) direction, in octahedral layer each cation coordination octahedra with two other with layer octahedron totally two ribs form the axial "the" shape chain of C, chain is connected with the "the" shape chain corner-sharing top of the top lower octahedral layer of interchain.Structural aberration can make Zn 2+ion affects antibacterial effect from the easier stripping of interlayer.
The present invention adopts sonochemistry precipitator method synthetic powder to be utilize it obviously to reduce synthesis temperature and Reaction time shorten, significantly changes the feature of grain morphology and size, reaches and control powder granule shape and size, improve the object of antibacterial effect.
The Antibacterial Mechanism of zinc tungstate antimicrobial powder can be summed up as Zn 2+the overlaying influence of the electrostatic adhesion sterilization mechanism of ion, active stripping Antibacterial Mechanism and photocatalysis antibacterial mechanism three aspects.
Feature of the present invention: be changed to foundation with streptococcus aureus test zinc tungstate antimicrobial powder antibacterial circle diameter, utilize simple Ultrasonic Heating condition synthetic antimicrobial nanometer Zn WO of good performance 4antimicrobial powder, can use under the envrionment conditions below 200 DEG C.The present invention's nanometer zinc tungstate compound replaces silver compound, has both reduced antiseptic-germicide cost, and has turn improved antibacterial effect.This process is simple, equipment requirements is low, environmental friendliness, and cheap, antibacterial effect is excellent.The present invention can be widely used in the field such as anti-bacteria paper and antimicrobial coating.
Summary of the invention
Adopt the nanometer zinc tungstate antimicrobial powder of technique simple sonochemistry precipitator method synthetic antimicrobial excellent property.It wants chemical reaction to be:
Na 2wO 4+ Zn (NO 3) 2=ZnWO 4↓+2NaNO 3(color of precipitation is white)
Above-mentioned reaction can be obtained by following technique:
Ultrasonic method prepares ZnWO 4antimicrobial powder (being called ZW1 below)
1) preparation of mixing solutions: by Na 2wO 4with Zn (NO 3) 2be mixed with the aqueous solution that concentration is 0.1-0.6mol/L respectively, then by Na 2wO 4solution slowly pours Zn (NO into 3) 2in the aqueous solution, make Na 2wO 4with Zn (NO 3) 2mol ratio be 1: 1-3, configure 60 ~ 150ml mixing solutions altogether;
2) ultrasonic method prepares ZnWO 4antimicrobial powder (being called ZW1 below)
Above-mentioned mixing solutions heats under Ultrasonic Conditions, and temperature is at 30-60 DEG C, and the reaction times is 10-50min, and this mixing solutions is fully mixed and completes chemical precipitation reaction, after mixing, in mixed solution, adularescent flocculent precipitate generates; After suction filtration mixed solution, remain throw out, then use distilled water and absolute ethanol washing throw out, dry 5-8h at 80-100 DEG C, can ZnWO be obtained 4antimicrobial powder, i.e. ZW1.
Preparation Ag 2wO 4method and above-mentioned technique all fours, be with sodium wolframate and Silver Nitrate for raw material, by the AW1 powder of above-mentioned technological process and the synthesis of the available sonochemistry precipitator method.
3) for reducing sintering temperature, obtain the higher zinc tungstate of degree of crystallinity and wolframic acid aluminium powder, the change of the powder that the zinc tungstate comparing the high stable form of degree of crystallinity is prepared with silver tungstate antibacterial performance and ultrasonic method, adopts following molten-salt growth method to prepare zinc tungstate and wolframic acid aluminium powder:
By above-mentioned ZW1 and composite fused salt (NaNO 3and LiNO 3) mass ratio be that 1: 3 mixed being incorporated in mortar adds appropriate dehydrated alcohol grinding 2h, ZW1 antimicrobial powder is fully mixed with reaction medium.Mixture loads in crucible, after drying 5h, is incubated 3h, obtains cured product after cooling after putting into inherent 210 DEG C, 240 DEG C, 270 DEG C, the 340 DEG C four kinds of temperature lower calcinations of electric furnace through 80 DEG C.With distilled water fully soak, absolute ethanol washing cured product, remove remaining fused salt, then through suction filtration, drying, zinc tungstate antimicrobial powder prepared by ultrasonic-molten-salt growth method can be obtained, i.e. ZW2.The preparation method being prepared AW2 by AW1 is similar with preparation ZW2; When the antibacterial circle diameter with streptococcus aureus test zinc tungstate and silver tungstate antibacterial powder, antibacterial circle diameter changes sees Fig. 1 and Fig. 2 and table 1 and table 2.
ZnWO obtained under table 1 differing temps 4color and antibacterial circle diameter
Ag2WO obtained under table 2 differing temps 4color and antibacterial ring width
It needs to be noted same processing condition, the zinc tungstate of preparation and the anti-microbial property of wolframic acid silver have a long way to go, and as table 1 and table 2, Fig. 1 and Fig. 2 is more known.The antibacterial circle diameter of ZW1 is 1.63 times of AW1.Along with calcining temperature improves, the germ resistance of ZW2 prepared by molten-salt growth method reduces greatly, and this can find out reason from Fig. 3 analysis; Fig. 3 (a) is ZW1 powder XRD figure, and display ZW1 is amorphous hump, does not have the diffraction peak of crystal, belongs to unformed powder or crystal defectiveness structure, and therefore its active large anti-microbial property is good.The XRD diffraction peak of Fig. 3 (b) ZW2 is strong, and degree of crystallinity is high, this be due to molten-salt growth method calcining after ZW2 degree of crystallinity better, generate stable state wolframite monoclinic form, activity greatly reduces and causes its Zn 2+not easily stripping, therefore antibacterial effect is also had a greatly reduced quality greatly.No matter be AW1 and AW2 as known from Table 2, wolframic acid aluminium powder antibacterial circle diameter all at about 12mm, antibacterial better heat stability, but anti-microbial property is in lower level compared with ZW1.From Fig. 4 wolframic acid silver XRD analysis, ultrasonic method and molten-salt growth method calcining after XRD be the very high diffraction peak of crystal structure degree, lower its antibacterial effect that makes of activity is poor; From Fig. 5, the SEM of ZW1 schemes the amorphous powder of ZW1 prepared by known ultrasonic method, and the random size of granule-morphology is at about 70nm.From Fig. 6 the SEM of ZW2 scheme known molten-salt growth method burn after ZW2 particle diameter about 50nm, granularity diminishes but degree of crystallinity is better, with reference to figure 3b, because its diffraction peak is strong, without assorted peak, crystal structure degree is good, generate stable state wolframite monoclinic form, anti-microbial property is reduced.Find out that AW1 crystal morphology is bar-shaped from the SEM figure of Fig. 7 and Fig. 8, size is at 0.1 μm × 2.5 μm; AW2 crystal morphology is column, and size is at 3-5 μm; Reference table 2 is known, and the size of crystal grain is little to antibacterial influential effect.Conclusion is low temperature when using, and can consider to replace AW1 with ZW1, the preparation technology of such as anti-bacteria paper the condition of 90-100 DEG C, namely available cheapness and the simple ZW1 of preparation technology.When comparatively high temps uses, do not advise the wolframic acid silver by this experimental technique condition, because its antibacterial circle diameter is less yet.Other effective antimicrobial powders can be adopted separately.
The anti-microbial property of silver is generally acknowledged, but the present invention to show the streptococcus aureus antibacterial effect of zinc tungstate for identical compared with wolframic acid silver compound really far from each other.This also tells us not every silver compound anti-microbial property is all much better than other compounds under any condition.This just needs us to find out suitable antimicrobial powder under different working conditions to suit the remedy to the case and to reduce costs.For with the change of golden staphylococci test antibacterial circle diameter in the present invention, the antibacterial effect of zinc tungstate is much larger than wolframic acid silver.This may be the AW powder better crystallinity degree prepared due to ultrasonic/ultrasonic-molten-salt growth method, active low, and relative solubility is lower, makes its anti-microbial property lower, and the AW2 that in addition prepared by ultrasonic-molten-salt growth method darkens, therefore to use be the requirement also will noting environment for use.
Accompanying drawing explanation
Fig. 1 is ultrasonic and ultrasonic-ZW1 for preparing of molten-salt growth method and differing temps under the antibacterial loop graph of ZW2
Fig. 2 is ultrasonic and ultrasonic-AW1 for preparing of molten-salt growth method and differing temps under the antibacterial loop graph of AW2
Fig. 3 is ultrasonic and ultrasonic-XRD figure of ZW1 and ZW2 prepared of molten-salt growth method; A ultrasonic method, b is ultrasonic-molten-salt growth method
Fig. 4 is ultrasonic and ultrasonic-XRD figure of AW1 and AW2 prepared of molten-salt growth method; A ultrasonic method, b is ultrasonic-molten-salt growth method
The SEM figure of the ZW1 of Fig. 5 ultrasonic preparation
Fig. 6 is ultrasonic-the SEM figure of ZW2 for preparing of molten-salt growth method
The SEM figure of the AW1 of Fig. 7 ultrasonic preparation
Fig. 8 is ultrasonic-and molten-salt growth method prepares the SEM figure of AW2
Embodiment
Embodiment 1:
The preparation of mixing solutions: by Na 2wO 4with Zn (NO 3) 2be mixed with the aqueous solution that concentration is 0.3mol/L respectively, then by Na 2wO 4solution slowly pours Zn (NO into 3) 2in the aqueous solution, make Na 2wO 4with Zn (NO 3) 2mol ratio be 1: 1, configure 100ml mixing solutions altogether;
Embodiment 2: ultrasonic method prepares ZnWO 4antimicrobial powder (being called ZW1 below)
Above-mentioned mixing solutions reacts 30min under Ultrasonic Heating condition, and temperature controls at about 40 DEG C, makes this mixing solutions fully react mixing, has fluffy white precipitate to generate after mixing in mixed solution.After suction filtration mixed solution, remain throw out, then with distilled water and dehydrated alcohol washing precipitate respectively, then under the condition of temperature 80 DEG C, dry 12h, can ZnWO be obtained 4antimicrobial powder, i.e. ZW1.

Claims (1)

1. the present invention is the nanometer zinc tungstate raw powder's production technology that a kind of anti-microbial property is better than wolframic acid silver, it is characterized in that the method comprises the following steps:
By Na 2wO 4with Zn (NO 3) 2be mixed with the aqueous solution that concentration is 0.1-0.6mol/L respectively, then by Na 2wO 4solution slowly pours Zn (NO into 3) 2in the aqueous solution, make Na 2wO 4with Zn (NO 3) 2mol ratio be 1: 1-3, configure 60 ~ 150ml mixing solutions altogether; Above-mentioned mixing solutions heats under Ultrasonic Conditions, and temperature is at 30-60 DEG C, and the reaction times is 10-50min, and this mixing solutions is fully mixed and completes chemical precipitation reaction, after mixing, in mixed solution, adularescent flocculent precipitate generates; After suction filtration mixed solution, remain throw out, then use distilled water and absolute ethanol washing throw out, dry 5-8h at 80-100 DEG C, can ZnWO be obtained 4antimicrobial powder; Its SEM shows that zinc tungstate particle shape is random, and be evenly distributed, diameter is at about 70nm; Its XRD shows that zinc tungstate powder prepared by ultrasonic method is amorphous state.
CN201410827894.1A 2014-12-29 2014-12-29 A kind of nanometer Zinc Tungstate raw powder's production technology of anti-microbial property better than wolframic acid silver Expired - Fee Related CN104591287B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410827894.1A CN104591287B (en) 2014-12-29 2014-12-29 A kind of nanometer Zinc Tungstate raw powder's production technology of anti-microbial property better than wolframic acid silver

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410827894.1A CN104591287B (en) 2014-12-29 2014-12-29 A kind of nanometer Zinc Tungstate raw powder's production technology of anti-microbial property better than wolframic acid silver

Publications (2)

Publication Number Publication Date
CN104591287A true CN104591287A (en) 2015-05-06
CN104591287B CN104591287B (en) 2017-07-11

Family

ID=53117404

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410827894.1A Expired - Fee Related CN104591287B (en) 2014-12-29 2014-12-29 A kind of nanometer Zinc Tungstate raw powder's production technology of anti-microbial property better than wolframic acid silver

Country Status (1)

Country Link
CN (1) CN104591287B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111317123A (en) * 2018-12-14 2020-06-23 解冰 Papaya enzyme composition for improving and promoting functions of digestive absorption system, preparation method and composite nano preparation
CN111317126A (en) * 2018-12-14 2020-06-23 解冰 Papaya enzyme composition for recovering and maintaining digestive function, preparation method and composite nano preparation
CN111317132A (en) * 2018-12-14 2020-06-23 解冰 Papaya enzyme composition for assisting in enhancing digestion and absorption functions of critically ill patients, preparation method and composite nano-preparation
CN112708299A (en) * 2020-11-30 2021-04-27 无锡境悠新材料科技有限公司 Preparation method of negative ion antibacterial after-finishing agent for wet grinding silver-zinc-tungsten-titanium composite system

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101983930A (en) * 2010-08-12 2011-03-09 河北联合大学 Method for preparing superfine zinc tungstate antibacterial agent by ultrasonic molten salt method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101983930A (en) * 2010-08-12 2011-03-09 河北联合大学 Method for preparing superfine zinc tungstate antibacterial agent by ultrasonic molten salt method

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111317123A (en) * 2018-12-14 2020-06-23 解冰 Papaya enzyme composition for improving and promoting functions of digestive absorption system, preparation method and composite nano preparation
CN111317126A (en) * 2018-12-14 2020-06-23 解冰 Papaya enzyme composition for recovering and maintaining digestive function, preparation method and composite nano preparation
CN111317132A (en) * 2018-12-14 2020-06-23 解冰 Papaya enzyme composition for assisting in enhancing digestion and absorption functions of critically ill patients, preparation method and composite nano-preparation
CN112708299A (en) * 2020-11-30 2021-04-27 无锡境悠新材料科技有限公司 Preparation method of negative ion antibacterial after-finishing agent for wet grinding silver-zinc-tungsten-titanium composite system
CN112708299B (en) * 2020-11-30 2022-07-22 无锡境悠新材料科技有限公司 Preparation method of negative ion antibacterial after-finishing agent for wet grinding silver-zinc-tungsten-titanium composite system

Also Published As

Publication number Publication date
CN104591287B (en) 2017-07-11

Similar Documents

Publication Publication Date Title
Zhao et al. Phase and morphological transitions of titania/titanate nanostructures from an acid to an alkali hydrothermal environment
CN101983930B (en) Method for preparing superfine zinc tungstate antibacterial agent by ultrasonic molten salt method
CN102139926B (en) Method for preparing nano oxide with high purity, high specific surface area and fine grains
CN104591287A (en) Preparation method of nano zinc tungstate powder with antimicrobial property superior to silver tungstate
Suwanboon et al. Physical and chemical properties of multifunctional ZnO nanostructures prepared by precipitation and hydrothermal methods
Dao et al. Effect of metal ion doping on the optical properties and the deactivation of photocatalytic activity of ZnO nanopowder for application in sunscreens
CN102513083A (en) Preparation method of diatomite loaded nano-zinc oxide composite powder material
CN103950985B (en) Nanometer bismuth tungstate of a kind of middle short side spherical structure and preparation method thereof
Wang et al. Biomimetic layer-by-layer deposition assisted synthesis of Cu, N co-doped TiO 2 nanosheets with enhanced visible light photocatalytic performance
CN105016382B (en) Method for preparing pure gold redstone type titanium dioxide nanorod
Chen et al. Visible-light-driven decomposition of antibiotic oxytetracycline and disinfection of Escherichia coli using magnetically recyclable lanthanum-nitrogen co-doped titania/calcium ferrite/diatomite heterojunction material
Hassanzadeh-Tabrizi Synthesis and characterization of nano Ce doped ZnO/γ-Al2O3 with improved photocatalytic activity
Torres-Martínez et al. Synthesis by two methods and crystal structure determination of a new pyrochlore-related compound Sm2FeTaO7
CN108545773B (en) Preparation method of nano titanium dioxide/tungsten trioxide composite material powder
CN104402050B (en) D phase hypovanadic oxide nanometer star powder and preparation method thereof
CN109502656B (en) Spherical Co (II) Co (III) hydrotalcite-like material and preparation method thereof
Ahmed et al. Influence of Zn/Fe molar ratio on optical and magnetic properties of ZnO and ZnFe 2 O 4 nanocrystal as calcined products of layered double hydroxides
CN104229878A (en) Preparation method of rutile crystal-form titanium dioxide nanorod
CN104585238B (en) Supersonic and co-deposition and ultrasonic molten-salt growth method prepare Ag2MoO4‑CuMoO4Compound antibacterial powder
Lee et al. Synthesis of ZnO nanoparticles via simple wet-chemical routes
CN103614139B (en) Reverse co-precipitation is adopted to prepare Gd 2ti 2o 7: the method for Ce nano-luminescent powder body
CN104386741B (en) A kind of preparation method of nanometer strip titanium dioxide of anatase crystal
Radhakrishnan et al. CuO nano structures as an ecofriendly nano photo catalyst and antimicrobial agent for environmental remediation
CN105036183A (en) Preparation method for nanometer Bi2Ti2O7 powder
Mehdizadeh et al. Synthesis and Characterization of β‐Co (OH) 2, CuO and ZnO Nanostructures by Solvothermal Method without Any Additive

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information

Address after: 063009 Hebei province Tangshan City Xinhua West Road No. 46

Applicant after: North China Polytechnics

Address before: 063009 Hebei province Tangshan City Xinhua West Road No. 46

Applicant before: Hebei United University

COR Change of bibliographic data
CB02 Change of applicant information
CB02 Change of applicant information

Address after: 063210 Tangshan City Road, Tangshan, Hebei Bay ecological city, Bohai Avenue, No. 21

Applicant after: North China Polytechnics

Address before: 063009 Hebei province Tangshan City Xinhua West Road No. 46

Applicant before: North China Polytechnics

GR01 Patent grant
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: 20170711

Termination date: 20181229