CN106317565A - Composition additive for laser marker - Google Patents
Composition additive for laser marker Download PDFInfo
- Publication number
- CN106317565A CN106317565A CN201610704782.6A CN201610704782A CN106317565A CN 106317565 A CN106317565 A CN 106317565A CN 201610704782 A CN201610704782 A CN 201610704782A CN 106317565 A CN106317565 A CN 106317565A
- Authority
- CN
- China
- Prior art keywords
- laser
- polymer
- color
- benzenesulfonic acid
- additive
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
The invention discloses a composition additive for a laser marker and belongs to the technical field of laser machining. The composition additive is prepared from one or a mixture of reaction products (or salts) of iron, nickel, cobalt, lead, tin, antimony or bismuth and p-toluenesulfonic acid (or homologous series), and a precursor, wherein the mol ratio of metal ions to a corresponding oxide and p-toluenesulfonate anion (or homologous series) is 1 to (2 to 6). According to a molecular design concept, a series of micro-granular laser marker additive composition for a shallow-color polymer is developed; the granular composition can be used for absorbing radiation of laser with the wavelength of 1.06 microns and enable micro-granules and a polymer thin layer covering the micro-granules to generate a decomposition reaction; and a deep-color product generated by decomposition can form a deep-color marker on the shallow-color polymer under the positive cooperative effect, and a two-dimensional image of the marker reaches a machine scannable identification grade.
Description
Technical field
The invention belongs to technical field of laser processing, especially according to new mechanism, the laser mark that obtains based on MOLECULE DESIGN
Note compositions of additives.
Background technology
The features such as Laser marking technology has at a high speed, efficient, energy-saving and environmental protection, have obtained extensively the most in the industrial production
Application, the manufacture field at plastics (polymer) goods has its unique advantage.Particularly laser labelling product produces than printing
The strong points such as product have length in service life, anti-scratch is drawn.The Nd:YAG pulse laser launching 1.06 mum wavelengths is commonly used for light color polymerization
The marking device of thing.Most polymer (P) are the highest for the light wave transmitance that wavelength is 1.06 μm, thus can not directly answer
Use laser technology mark.Laser marking additives (A) is added in the polymer for this.For improving laser labelling efficiency, permissible
Synergist (I) is added in A.Such as: it is Sb that US4816374 discloses A2O3, its consumption is the 2%-6% of P, and CN1152911 drapes over one's shoulders
Dew when addition 0.3%-3% pearlescent pigment I after, Sb2O3Consumption be 0.5%-5%；US7169471, A are BiOCl, and I is many
Plant Organic substance；CN102597081, A are Bi2O3；I is bismuth citrate；US7187396, A are ATO, and I is PETG；Etc..In technique
On, A, I and P are mixed by blending technology machine-shaping, therefore they broadly fall into the synergisting method of physical modification.
Document: Beijing University of Technology Yang Wei's in 2010 is entitled: " plastic surface laser marking and the research of variable color technique "
Master's thesis, the mechanism of action of the report A such as US6693657, US8877332 be: when laser beam irradiation is to when being added with the P of A,
Particulate A absorbs laser radiation energy and luminous energy is changed into heat energy, heats itself and is wrapped in the polymer thin on its surface
The tiny area of layer, is allowed to temperature and drastically raises, cause this polymer foil generation pyrolysis, product carbon and carbonization
Thing forms the labelling of dark color in low color polymers；Owing to overwhelming majority laser marking additives microgranule is in the inside of P, above-mentioned
Document has all been reported carburizing reagent and has been occurred in the inside of polymer.According to this mechanism, between laser marking additives microgranule and P
Effect should be to carry out between their contact interface.Contribution to labelling colour generation is by thermal decomposition product (carbon and the carbon of P
Compound) make.
Summary of the invention
The present invention in order to overcome above-mentioned the deficiencies in the prior art,
A kind of compositions additive for laser labelling, by ferrum, nickel, cobalt, lead, stannum, antimony or bismuth p-methyl benzenesulfonic acid (or
Its homologue) the mixture of one or several of product (or salt) and precursor composition, wherein metal ion is right with it
The oxide answered is (with molecular formula MO, M2O3Or MO2Represent) and the mol ratio of p-methyl benzenesulfonic acid root (or its homologue): 1:2-6；
Wherein M is ferrum, nickel, cobalt, lead, stannum, antimony or bismuth.
The preparation method of above-mentioned a kind of compositions additive for laser labelling, is carried out: metal oxygen as steps described below
It is evaporated after compound (or hydration of its oxide) and p-methyl benzenesulfonic acid (including its homologue) reacting by heating in aqueous, then
Dry 30min, cool down, be milled down to D50 between 10-50um for 110 DEG C-140 DEG C.
Advantages of the present invention: this technology utilizes the compositions additive of laser labelling in the laser action that wavelength is 1.06 μm
Issue raw intramolecular chemical reaction, thus not only Energy harvesting is abundant, reaction is quick；And the compositions of laser labelling adds
Add agent reaction dark product can be wrapped in the thermal decomposition product of polymer foil on additive particulate surface in positive coorperativity
Under effect so that the color ratio of formation labelling is deeper when not having intramolecule to react；Therefore add small amount and (refer in A contained
The amount of metal) the two-dimension code pattern that obtains through mark of the polymer of the described A through chemical modification just can reach machine
Can scanning recognition level.
Detailed description of the invention
It is contemplated that:
If the interparticle making A contains the compound that the laser emission that absorbable wavelength is 1.06 μm is decomposed, owing to changing
Reaction within adduct molecule need not mass transfer and diabatic process, thus can be greatly enhanced the efficiency of reaction；If set again
Meter makes the intramolecular dark product thermally decomposed to yield and is wrapped in the polymer foil generation heat point on additive particulate surface
Solve and react the dark product (carbon and carbide) obtained in positive coopertive effect, it is possible to obtain more dark labelling.Based on so
Thinking, the present invention proposes the class microgranular laser marking additives compositions for low color polymers.This programme micro-
Containing p-methyl benzenesulfonic acid (including its homologue) root in granular composition, also contain the metals such as ferrum, nickel, cobalt, lead, stannum, antimony, bismuth simultaneously
Ion；Owing to p-methyl benzenesulfonic acid (including its homologue) is a strong acid, it can be easy to and above-mentioned metal or semimetal oxygen
Compound reaction generates p-methyl benzenesulfonic acid (including its homologue) salt；In molecular structure, (O/ (C+H)) and (atomic ratio) of (O/C) are little
Local response district is kept to be in strong reducing property environment in high-temperature hot is reacted to being enough to make it.When under laser irradiation, local anti-
Answering district to be under strong reducing property environment, reaction obtains following product: 1. element sulphur will be reduced and and metallic atom generation dark color
Sulfide；The least (O/C) (atomic ratio) makes to produce in pyrolysis residual carbon.So, the thermal decomposition product-carbon of P and A
Thermal decomposition product-dark color sulfide, carbide and carbon residue, under positive coopertive effect so that formed labelling color ratio do not have
Intramolecule is deeper when reacting；Therefore add what the less amount of described polymer through the A of chemical modification obtained through mark
Two-dimension code pattern just can reach machine-scannable identification level.
Obviously, the mechanism of this particulate composition is that the optical and thermal within the compound molecule within additive particulate is divided
Solve reaction and the pyrolysis within additive particulate is carried out simultaneously, make along with the heating by additive particulate to be wrapped in
The pyrolysis of its outer polymer；Obviously it is not affected by the kind and structure being wrapped in its outer polymer, thus
Can be suitably used for any kind polymer or the mixture of polymer, such as thermoplastic resin, thermosetting resin and elastomer.?
In the case of polymer is thermosetting resin, precursor polymer being also suitable them and combinations thereof thing.The most this intramolecule
Reaction need not heat transfer and mass transport process, therefore ratio needs have more rapid, the energy of reaction by heat transfer and the additive of mass transfer
Amount utilizes more efficient feature.
From above-mentioned mechanism it will also be appreciated that along with the increase of bombardment with laser beams energy, the temperature of additive particulate will be higher,
Decomposition reaction will be fiercer, and the color of labelling can be deeper；The operating distance degree of the thin layer of the microgranule P to being wrapped in outside it is also simultaneously
To increase, the area of the speckle obtained also will be enlarged by, consequently, it is possible to make the resolution of labelling or definition reduce.
The foundation of the present invention:
1 as described in above-mentioned document, and laser marking additives microgranule is in by the state of polymer wrapped, therefore at laser
The extremely short moment of impulse action can be laser marking additives particulate composition and the polymer thin being wrapped in its surface
The tiny area of layer regards an isolated system as, and its discord air exists mass transfer and diabatic process.
In the molecular structure of p-methyl benzenesulfonic acid (including its homologue) salt such as 2 ferrum, nickel, cobalt, lead, stannum, antimony, bismuth (O/C+H)
(O/C) (atomic ratio) is small enough to make it set up strong reducing property environment in local response region in high-temperature hot is reacted；
In such a case, their thermal decomposition product has: the sulfide that (1) element sulphur will be reduced also and metallic atom generation is coloured；
The least (O/C) (atomic ratio) makes pyrolysis not only set up strong reducing property environment, and produces carbide and residual carbon.
The existence of 3 residual carbon confirms the mechanism described in above-mentioned 1 and 2 the most in turn.
The sulfide of the thermal decomposition product of 4 above-mentioned p-methyl benzenesulfonic acid (including its homologue) salt-coloured, carbon (include carbonization
Thing) and the heated reaction product carbon (including carbide) of polymer, under positive coopertive effect so that the color ratio of the labelling of formation
The color of the carbon only thermally decomposed to yield by polymer is deeper.
The present invention is to realize above-mentioned technical purpose by techniques below means.
P-methyl benzenesulfonic acid (includes its homologue): benzenesulfonic acid, toluene sulfonic acide, acid dimethyl and detergent alkylate sulphur
Acid is all the strongest acid；They directly can react generate salt with basic anhydride.Pass through Acid-Base reaction on market to close
The benzene sulfonate supplies of commodities such as the copper p-toluenesulfonate become, p-methyl benzenesulfonic acid ferrum, and DBSA ferrum；Document has been reported
The method leading copper dodecylbenzenesulphate.They be all by after corresponding Acid-Base direct reaction in aqueous through concentrating, knot
Brilliant, be dried to obtain.Because p-methyl benzenesulfonic acid (including its homologue) is strong acid, even if above-claimed cpd does not has commodity, do not has yet
Reported in literature, utilizes acid-base reaction to prepare above-claimed cpd and the most should there is not technical difficulty.Antimony oxide is ferrum, nickel,
Cobalt, antimony, bismuth, lead, the most weak one of the oxide neutral and alkali such as stannum, it is also in Acid-Base and worst one of salt-forming reaction activity；
Therefore, by as a example by the product of p-methyl benzenesulfonic acid and antimony oxide, can demonstrate again that above-mentioned oxide can be with
P-methyl benzenesulfonic acid (including its homologue) carries out salt-forming reaction.Through to p-methyl benzenesulfonic acid and the XRD analysis of antimony oxide product,
When p-methyl benzenesulfonic acid relative usage increases, the intensity of the spectral line of antimony oxide reduces so that disappearing (seeing attached list 1), in spectrogram
See one group of spectral line that can not belong to antimony oxide, although on document, do not have the spectral line of p-methyl benzenesulfonic acid antimonic salt to be available for comparison
Relatively, but according to the kind that feeds intake, rate of charge and reaction principle, it is only possible to be antimony oxide and p-methyl benzenesulfonic acid reaction life
The salt become；The above-mentioned spectral line not belonging to antimony oxide is only possible to the reaction being to belong to p-methyl benzenesulfonic acid and antimony oxide
The spectral line of product.
The preparation of laser marking additives microgranule:
P-methyl benzenesulfonic acid (including its homologue) is strong acid, can be with oxide (or hydrate of its oxide) water-soluble
Liquid is evaporated after reaction, then dries 30min at 110 DEG C-140 DEG C, cool down, be milled down to D50 between 10-50um.
The preparation of mark sample and performance measurement:
With conventional method be blended, polymer containing laser marking additives particulate composition made by pelletize, tabletting
Test piece.
The model produced with Suzhou Kai Tai laser Science and Technology Ltd. is the laser marking machine mark of KDD-50 institute.The work of mark
Skill condition: electric current: 9-13A；Scanning speed: 500-2000mm/min.
Aberration is measured with the color difference meter that model is 7000A of X. Rite Inc. of the U.S..According to the CIE Lab colour space, from survey
Obtain the Δ L, Δ a and Δ b of labelling, be calculated Δ E.According to reported in literature, when the total color difference Δ E > 4 of labelling, this labelling
It is distinguished.
From to the Δ E statistics of the labelling obtained under the conditions of different marks and and the word of 15 × 15mm be:
The possibility that the image in 2 D code of " cczu.edu.cn " is known in machine scans, has a following rule:
1 requires certain aberration at machine scans identification image in 2 D code；
The 2 mark electric currents improved can obtain higher aberration；
The mark electric current (power) that 3 improve as previously mentioned may make the definition of the unit of composition diagram picture decline, and affects machine
The possibility of device scanning recognition；
As it was previously stated, the mechanism of action of physical modification is: react between the interface of A, I and P, the biography of this reaction
The resistance of matter and heat transfer is the most relatively large, and labelling is made the contribution of colour generation based on the thermal decomposition product of P.
The following is the embodiment of this technology.
Embodiment 1
By Sb2O3: p-methyl benzenesulfonic acid=1:2 (mol ratio) obtains compositions in (110 DEG C) reaction.Polymer P E.Mark is swept
Retouch speed: 500mm/s.The polymer of addition particulate composition color after processing: white.
Test result
Embodiment 2
By Sb2O3: 125 DEG C of reactions of p-methyl benzenesulfonic acid=1:4 (mol ratio) obtain compositions.Polymer P E.Mark scanning speed
Degree: 500mm/s.The polymer of addition particulate composition color after processing is still white.
Test result
Comparative example data
Comparative example 1, embodiment 2 and comparative example data can confirm that with p-methyl benzenesulfonic acid modification Sb2O3Identical
Sb2O3The Δ E of labelling can be significantly increased under content；Particularly in additive, p-methyl benzenesulfonic acid radical content is high than low effect
More notable.Embodiment 3
By Bi2O3: 110 DEG C of reactions of p-methyl benzenesulfonic acid=1:2 (mol ratio) obtain compositions.Polymer P E.Mark scanning speed
Degree: 500mm/s.The polymer of addition compositions color after processing: white.
Test result
| Composition levels/% | Bi2O3Content % | It is applicable to the mark electric current/A of machine scans identification image in 2 D code |
| 0.4 | 0.23 | 11-13 |
Embodiment 4
By Bi2O3: 110 DEG C of reactions of p-methyl benzenesulfonic acid=1:2 (mol ratio) obtain compositions.Polymer TPU.Compositions contains
Amount: 0.4/%；Bi2O3Content: 0.23%.
The polymer of addition compositions color after processing: white.
Test result
Embodiment 5
By Bi2O3: p-methyl benzenesulfonic acid=1:4 (mol ratio) obtains compositions 110 DEG C of reactions.Polymer TPU.Compositions
Content: 0.4/%；Bi2O3Content: 0.17%.Mark scanning speed: 500mm/s.Add the polymer of compositions after processing
Color: white.
Test result
| Mark scanning speed mm/min | It is applicable to the mark electric current/A of machine scans identification image in 2 D code |
| 500 | 9-13 |
| 1000 | 10-13 |
Embodiment 6
By Bi2O3: p-methyl benzenesulfonic acid=1:6 (mol ratio) obtains compositions 110 DEG C of reactions.Polymer P E.Mark scans
Speed: 500mm/s.The polymer of addition compositions color after processing: white.
Test result
| Composition levels/% | Bi2O3Content % | It is applicable to the mark electric current/A of machine scans identification image in 2 D code |
| 0.4 | 0.13 | 13 |
Embodiment 7
By Fe2O3: p-methyl benzenesulfonic acid=1:4 (mol ratio) obtains compositions 140 DEG C of reactions.Composition levels:
0.4/%；Fe2O3Content: 0.083%.Polymer P E.The polymer of addition compositions color after processing is light brown red.
Test result
| Mark scanning speed mm/min | It is applicable to the mark electric current/A of machine scans identification image in 2 D code |
| 500 | 11-13 |
| 1000 | 13 |
Subordinate list 1 p-methyl benzenesulfonic acid and antimony oxide reaction obtain the XRD spectral line of compositions and compare
In table, with 1, RI represents that RI is the strongest, and weakens according to the increasing of numeral.
Claims (2)
1. the compositions additive for laser labelling, it is characterised in that by ferrum, nickel, cobalt, lead, stannum, antimony or bismuth to first
The mixture of one or several of the product (or salt) of benzenesulfonic acid (or its homologue) and precursor composition, wherein metal from
Son with the oxide of its correspondence (with molecular formula MO, M2O3Or MO2Represent) and p-methyl benzenesulfonic acid root (or its homologue) mole
Ratio: 1:2-6；Wherein M is ferrum, nickel, cobalt, lead, stannum, antimony or bismuth.
2. the preparation method of a kind of compositions additive for laser labelling described in the claims 1, it is characterised in that
Carry out as steps described below: metal-oxide (or hydration of its oxide) and p-methyl benzenesulfonic acid (including its homologue) are water-soluble
Liquid is evaporated after reacting by heating, then dries 30min at 110 DEG C-140 DEG C, cool down, be milled down to D50 between 10-50um.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610704782.6A CN106317565B (en) | 2016-08-22 | 2016-08-22 | A kind of composition additive for laser labelling |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610704782.6A CN106317565B (en) | 2016-08-22 | 2016-08-22 | A kind of composition additive for laser labelling |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106317565A true CN106317565A (en) | 2017-01-11 |
| CN106317565B CN106317565B (en) | 2019-07-26 |
Family
ID=57741421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610704782.6A Expired - Fee Related CN106317565B (en) | 2016-08-22 | 2016-08-22 | A kind of composition additive for laser labelling |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106317565B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107057301A (en) * | 2017-05-13 | 2017-08-18 | 广东圆融新材料有限公司 | A kind of fire-retardant reinforced PBT composite material of excellent laser printing effect and preparation method thereof |
| CN110590611A (en) * | 2019-09-11 | 2019-12-20 | 常州大学 | Laser marking additive and preparation method and application thereof |
| CN113621150A (en) * | 2021-08-20 | 2021-11-09 | 江苏澳盛复合材料科技有限公司 | Carbon fiber reinforced polycarbonate composite material and molded product prepared from same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101039997A (en) * | 2004-10-15 | 2007-09-19 | 化学制造布敦海姆两合公司 | Pigment for laser-writable plastic materials and use thereof |
| CN101987922A (en) * | 2009-08-04 | 2011-03-23 | 三星Total株式会社 | Resin composition for a white laser marking |
| CN102356131A (en) * | 2009-03-18 | 2012-02-15 | 默克专利股份有限公司 | Pigment for laser marking |
-
2016
- 2016-08-22 CN CN201610704782.6A patent/CN106317565B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101039997A (en) * | 2004-10-15 | 2007-09-19 | 化学制造布敦海姆两合公司 | Pigment for laser-writable plastic materials and use thereof |
| CN102356131A (en) * | 2009-03-18 | 2012-02-15 | 默克专利股份有限公司 | Pigment for laser marking |
| CN101987922A (en) * | 2009-08-04 | 2011-03-23 | 三星Total株式会社 | Resin composition for a white laser marking |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107057301A (en) * | 2017-05-13 | 2017-08-18 | 广东圆融新材料有限公司 | A kind of fire-retardant reinforced PBT composite material of excellent laser printing effect and preparation method thereof |
| CN107057301B (en) * | 2017-05-13 | 2019-04-19 | 广东圆融新材料有限公司 | A kind of fire-retardant reinforced PBT composite material and preparation method thereof of excellent laser printing effect |
| CN110590611A (en) * | 2019-09-11 | 2019-12-20 | 常州大学 | Laser marking additive and preparation method and application thereof |
| CN110590611B (en) * | 2019-09-11 | 2021-11-02 | 常州大学 | Laser marking additive and preparation method and application thereof |
| CN113621150A (en) * | 2021-08-20 | 2021-11-09 | 江苏澳盛复合材料科技有限公司 | Carbon fiber reinforced polycarbonate composite material and molded product prepared from same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106317565B (en) | 2019-07-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Miao et al. | Hetero-atom-doped carbon dots: Doping strategies, properties and applications | |
| CN106317565A (en) | Composition additive for laser marker | |
| Abdulwahid et al. | The study of structural and optical properties of PVA: PbO 2 based solid polymer nanocomposites | |
| Dang et al. | Pyromellitic acid-derived highly fluorescent N-doped carbon dots for the sensitive and selective determination of 4-nitrophenol | |
| CN101039997B (en) | Pigment for laser-writable plastic materials and use thereof | |
| CN109963702B (en) | Additives for laser-markable and laser-weldable polymer materials | |
| CN105713288B (en) | One kind turns light conversion farm film and preparation method and application | |
| CN107075260B (en) | Laser-markable and laser-weldable polymer material | |
| CN107849290B (en) | Laser markable polymers and coatings | |
| CN101475217A (en) | Method for preparing pigment grade chromium hemitrioxide green by using gaseous reducing agent low temperature reduction chromate salt | |
| CN104401981A (en) | Preparation method of nitrogen-containing oxidative graphene quantum dot capable of giving off fluorescence in three primary colors | |
| CN106892460B (en) | A kind of preparation method of tungsten bronze nanometer sheet | |
| RU2666872C1 (en) | Doped copper (ii) hydroxide-phosphate, method for producing same and use thereof | |
| Li | Solid state synthesis and luminescence of NaLa (WO 4) 2: Dy 3+ phosphors | |
| TW201842073A (en) | Antimony free composition for laser marking thermoplastic compounds | |
| CN105154069A (en) | Multi-colored adjustable light-emitting material of nitrogen-doped carbon dot coordination rare earth and preparation method thereof | |
| Pering et al. | Investigation of solution-based synthesis of non-toxic perovskite materials using Mg, Ca, Mn, Fe, Cu, and Zn as the B-site cation for photovoltaic applications | |
| Wang et al. | Solvothermal preparation of nitrogen and phosphorus-doped carbon dots with PET waste as precursor and its application | |
| CN111718557B (en) | Polymer/modified organic montmorillonite laser marking material and preparation method and antibacterial application thereof | |
| JP5028213B2 (en) | Additive for laser marking | |
| CN110144050B (en) | With MnO4-Rare earth europium coordination polymer with detection function and preparation method thereof | |
| KR100618083B1 (en) | Invisible-Light Absorption Material and Ink and Manufacturing Method of the same | |
| CN115595145A (en) | Preparation method and application of nitrogen-zinc doped carbon dot-hydrotalcite nanocomposite | |
| CN112119128B (en) | Laser additives and their use in polymeric materials | |
| CN101468398A (en) | Method for producing nano-scale yellow copper structure powder and polymer thin-film solar cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190726 Termination date: 20210822 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |