CN102796215A - Preparation method of peeled-up yellow-light hydrotalcite like/polymer nanocomposite - Google Patents
Preparation method of peeled-up yellow-light hydrotalcite like/polymer nanocomposite Download PDFInfo
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- CN102796215A CN102796215A CN2012102817709A CN201210281770A CN102796215A CN 102796215 A CN102796215 A CN 102796215A CN 2012102817709 A CN2012102817709 A CN 2012102817709A CN 201210281770 A CN201210281770 A CN 201210281770A CN 102796215 A CN102796215 A CN 102796215A
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Abstract
The invention relates to a preparation method of a peeled-up yellow-light hydrotalcite like/polymer nanocomposite, comprising the following steps: firstly respectively prefabricating an aluminium chloride solution A and a mixed solution B of zinc chloride and magnesium chloride, and then mixing a ligand with sodium stearate to prepare a mixed slurry C; under the effect of strong stirring or supersonic waves, simultaneously adding the solution A and the solution B dropwisely in the mixed slurry C, adjusting the pH value, aging, washing sediments, then conducting pumping filtration, and frying a filter cake to obtain a strong-fluorescent yellow-light hydrotalcite like; immersing the yellow-light hydrotalcite like in a polymer monomer and an initiator for 24h, then conducting microwave radiation polymerization for 3min to obtain the peeled-up yellow-light hydrotalcite like/polymer nanocomposite. The peeled-up yellow-light hydrotalcite like/polymer nanocomposite prepared by the method has good luminescence performance of original metal complex, and has the advantages of easy forming, strong shock resistance, light weight, low cost, easy film forming and the like of organic polymer materials.
Description
Technical field
The invention belongs to the photovaltaic material technical field, be specifically related to one type of preparation method, and relate to the application of said material in fields such as pl-, electroluminescent with exfoliated gold-tinted acrylic/hydrotalcite-like nano matrix material of fluorescent characteristic.
Technical background
The simplest general formula is [M
2+ 1-xM
3+ x(OH)
2] A
N- X/n.mH
2(layered double hydroxides LDHs), is one type of mixed metal hydroxides with unique layered crystal structure to the hydrotalcite of O, M in its flaggy
2+Be divalent cations such as Mg, Ni, Cu or Zn, M
3+Be isomorphous Tricationic such as Al
3+Deng, A
N-For the interlayer valency is-negatively charged ion such as the CO of n
3 2-, Cl
-, SO
4 2-, NO
3 -Or other organic anion, subscript refers to the content of metallic element, x=n (M
3+): [n (M
2+)+n (M
3+)], value between 0. 2～0. 33, i.e. n (M
2+)/n (M
3+)=2～4, m is the hydration water number.Because M
2+Partly by M
3+Make the hydrotalcite flaggy positively charged behind the isomorphous substitution, the negatively charged ion between interposed layer links to each other with flaggy with weak chemical bond, with positive charge excessive on the balance flaggy, and is filled into interlayer with the water molecules of some amount.Because the cationic substitutability of flaggy of LDHs and the commutability of interlayer anion; Can be with various inorganic with organic anion, with in many and the interposed layer such as heteropolyanion and title complex negatively charged ion; Assembling obtains the stratiform thing of supramolecular structure; Can obtain thus different series intercalation houghite material (hydrotalcite-like compound, HTLc).So far, the various countries investigator is to synthetic, the preparation method of LDHs and HTLc, and carried out broad research at aspects such as IX, absorption, separation, catalysis, medicine and explored with using.
In recent years, the preparation of various functional houghites and characteristic research particularly receive publicity.Because the rare earth of special electron structure of tool and various multivalence, the transition metal that appraises at the current rate have functions such as various light, electricity, magnetic, catalysis; Therefore rare earth and multivalence, the transition metal ion that appraises at the current rate are introduced in the hydrotalcite structure to obtain functional houghite, become one of focus of hydrotalcite research field.People such as Duan Xue in 2005 propose the patented claim (number of patent application: 200510012245.7 of " having rare earth compounding intercalated houghite of fluorescent characteristic and preparation method thereof "; Publication number: CN1715365A), tie up to hydrotalcite layers introduces rare earth ion such as Eu through IX ammonia carboxylic title complex to obtain the epipolic hydrotalcite of tool.In addition, L. Latterini etc. insert hydrotalcite layers with azo class and other dyestuff through IX, and acquisition has the hybrid material of light, electric work ability.
As everyone knows; Oxine zinc class coordination compound with wide excitation band and high fluorescence efficiency; Fluorescence metal title complex as one type of excellent combination property; Be used for one of fluorescent material of luminous or display device always by first-selection, be still its difficult problem of further using of puzzlement so far but its light, poor heat stability are difficult to problems such as big area film forming, cost height, and become the focus that the investigator pays close attention to.
Summary of the invention
The object of the present invention is to provide the preparation method of the discrete gold-tinted houghite/polymer composites of a kind of height; Pass through coprecipitation method; Introduce oxine zinc class coordination compound in the inorganic magnesium aluminum-hydrotalcite with good luminous performance; And, obtain highly discrete matrix material fast through the microwave polymerization, the hydrotalcite flaggy is dispersed in the polymeric matrix; Obtain Heat stability is good, forming process is easy, strong shock resistance, in light weight, cost is low, be prone to film forming fluorescent functional material.
The present invention is with an amount of divalent zinc ion (Zn
2+) part replaces the divalence mg ion (Mg in the magnesium aluminum-hydrotalcite flaggy
2+), use the tensio-active agent StNa to bring oil loving oxine or derivatives thereof into the magnesium aluminum-hydrotalcite interlayer simultaneously, make its with the metal hydroxides flaggy that disperses to be embedded in magnesium aluminum-hydrotalcite on zine ion (Zn
2+) coordination, so, parts such as oxine because of with zine ion (Zn
2+) coordination and " suspension " on oxyhydroxide flaggy surface and each unit by isolated fixing on it; Thereby assembling, a kind of special ligand complex structure that is different from former coordination compound fully of formation; Because this special construction has the bigger structural asymmetry of oxine zinc class coordination compound of specific ionization or " freedom ", thereby can improve the fluorescence efficiency of its luminescence center; In addition, because divalent zinc ion (Zn wherein
2+) be to disperse, be fixed on the flaggy, thereby can effectively prevent the quenching of fluorescence that each luminescence unit causes because of reunion; Simultaneously because the provide protection of such hydrotalcite layered structure; Can improve its thermostability, can send than the corresponding oxine zinc class coordination compound gold-tinted houghite (Zn-HTLc) of hyperfluorescence more thereby obtain different with common non-blooming magnesium aluminum-hydrotalcite or zinc-aluminium hydrotalcite one type., as precursor it is soaked in the polymer monomer with this, obtains the exfoliated gold-tinted houghite/polymer nanocomposites of high fluorescence through the microwave polyreaction.
Following for realizing the present invention preparation method that synthetic exfoliated gold-tinted houghite/the polymer nanocomposites purpose adopts:
1, the preparation of gold-tinted houghite
1) preformulation of reactant
With aluminum chloride (AlCl
3) be dissolved in the deionized water, be mixed with solution A;
With magnesium chloride (MgCl
2) and zinc chloride (ZnCl
2) be dissolved in respectively in the deionized water, remix becomes solution B;
Molten the mixing of part is mixed with mixed serum C in StNa.
In the described solution B, Mg
2+: Zn
2+Mol ratio be 1:0.04～0.13.
Mg in the described solution B
2+With the Al in the solution A
3+Mol ratio be 1:0.097～0.31.
Described part is oxine or oxine verivate, Zn
2+: the mol ratio of part is 1:2.
Dissolve the mixing in advance of said part is meant in advance the part dissolving or is dispersed in the tensio-active agent StNa.Dissolving the purpose of mixing in advance is to make oil loving part more be prone to insert the magnesium aluminum-hydrotalcite interlayer in the process in order to prepare in coprecipitation method.Mg
2+: the mol ratio of StNa is 1:0.04～0.3.
2) under violent stirring or UW effect; Simultaneously solution A and solution B are dropwise added among the mixed serum C, with sodium hydroxide solution conditioned reaction mixed serum to pH=9～13, in 60～80 ℃ of following ageings 9～12 hours; Suction filtration, water washing filter cake are to pH=7～8 of filtrating eventually; Suction filtration behind the washing precipitate, filter cake was dried 2 hours down in 100～110 ℃, obtained the gold-tinted houghite of hyperfluorescence.
2, the preparation of exfoliated gold-tinted houghite/polymer nanocomposites
The gold-tinted houghite of last step preparation was soaked in pretreated polymer monomer and the initiator after 24 hours, places microwave, microwave frequency 2.45GHz, polymerization time 3 minutes promptly gets exfoliated gold-tinted houghite/polymer nanocomposites.
Described pretreated polymer monomer is meant TEB 3K, vinylbenzene or aniline.
Described initiator is meant Diisopropyl azodicarboxylate, Potassium Persulphate, BPO or ammonium persulphate.
Among the present invention, the mass ratio of gold-tinted Lei Shui Hua Shi ︰ polymer monomer is 1:5.5～19; The quality of initiator is 5% of a polymer monomer quality.
Above-mentioned materials is carried out fluorescence spectrum, IR and XRD analysis proof obtained title product.
Adopt preparation method of the present invention, have 1, preparation condition is gentle; 2, equipment is simple; 3, synthetic advantage fast.
Description of drawings
Fig. 1 is the fluorescence emission spectrogram of gold-tinted houghite (b) among the embodiment 1, corresponding zine coordination compound (a) and exfoliated gold-tinted houghite/polymer nanocomposites (c).
Fig. 2 is the XRD comparison diagram of gold-tinted houghite (b) and exfoliated gold-tinted houghite/polymer nanocomposites (c) and pure water talcum (d) among the embodiment 1, and wherein illustration is corresponding low angle diagram.
Fig. 3 is a pure water talcum (d) among the embodiment 1, the FT-IR spectrogram of gold-tinted houghite (b) and exfoliated gold-tinted houghite/polymer nanocomposites (c).
Embodiment
Below the preparation method of exfoliated gold-tinted houghite/polymer nanocomposites of the present invention is described further, will helps understanding the present invention and advantage thereof with indefiniteness embodiment, and not as to qualification of the present invention.
Embodiment 1
1, takes by weighing 0.061 gram AlCl
3Be dissolved in the deionized water, be mixed with solution A;
2, take by weighing the MgCl of 0.14 gram
2ZnCl with 0.013 gram
2Be dissolved in respectively in the deionized water, remix becomes solution B;
3, take by weighing 0.06 gram 2-biphenyl-oxine is poured into after with anhydrous alcohol solution in the aqueous solution that contains 0.04 gram StNa, be mixed with mixed serum C;
4, under violent stirring; Simultaneously solution A and solution B are dropwise added among the mixed serum C, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to pH=12, in 80 ℃ of following ageings 9 hours; Suction filtration, water washing filter cake are to the pH=7.5 that filtrates; With suction filtration behind a small amount of soaked in absolute ethyl alcohol, the washing precipitate, filter cake obtains gold-tinted houghite sample in 100 ℃ of oven dry down.This fluorescent emmission spectrum figure is shown in the curve b among Fig. 1.
5, get this gold-tinted houghite 0.1 gram; Add in pretreated TEB 3K of 1.8 grams and the 0.09 gram Diisopropyl azodicarboxylate; Fully soak and mix after 24 hours, place microwave, microwave frequency 2.45GHz; Polymerization time 3 minutes promptly gets exfoliated gold-tinted houghite/polymer nanocomposites.This nano composite material fluorescence emission spectrogram is shown in the curve c among Fig. 1, and the fluorescence emission spectrogram of corresponding zine coordination compound is shown in the curve a among Fig. 1.
Visible by Fig. 1; The gold-tinted houghite emission peak similar with zine coordination compound occurred at 554nm; And fluorescence intensity is stronger; Explain that the gold-tinted houghite keeps and strengthened the luminescent properties of zine coordination compound, and exfoliated gold-tinted houghite/polymer nanocomposites has still kept the photoluminescent property similar with zine coordination compound.
Visible by Fig. 2; Compare with the pure water talcum, (003) diffractive features peak of gold-tinted houghite is moved to the left, and the laminate spacing increases to 1.6nm by pure water steatitic 0.77nm; Show that part has got into interlayer; Near 2 θ were 60 °, near the position of (110) diffraction peak 2 θ are 60 ° did not have to change d basically
110Data are approaching, explain that two kinds of hydrotalcite laminate electric density do not change, and the hydrotalcite laminate obtains more complete maintenance.And in exfoliated gold-tinted houghite/polymer nanocomposites, the characteristic diffraction peak of hydrotalcite disappears basically, the steamed bun peak of PMMA only near 16 °, occurs, and demonstration hydrotalcite lamella is fully peeled off, and is scattered in the PMMA matrix.
Visible by Fig. 3, the absorption peak of gold-tinted houghite has also produced a series of new peak, wherein 2972cm except containing all charateristic avsorption bands of pure water steatitic
-1, 2925 cm
-1The absorption peak at place belongs to the v of methyl and methylene radical
C-HStretching vibration is simultaneously at 1263cm
-1The place has produced carboxylic acid group's v
C-OStretching vibration peak shows that fatty acid radical is between interposed layer; 1378 cm
-1Be the stretching vibration peak of the C-N key of part, show that nitrogen-atoms participated in Cheng Jian, caused C-N key stretching vibration intensity to increase; 861 cm of fingerprint region
-1With 720 cm
-1Two absorption peaks have shown that the existence of isolating H and five H that link to each other is arranged, and have proved that part has inserted interlayer; 1069cm
-1Belong to the C-O stretching vibration among the Zn-O-C, 447 cm
-1Belong to the stretching vibration of the Zn-O among the Zn-O-C, shown the zinc ion coordination success on interlayer part and the laminate.And in exfoliated gold-tinted houghite/polymer nanocomposites, except the absorption peak that contains the gold-tinted houghite, at 1735cm
-1The C=O absorption band of representative examples of saturated aliphatic ester has appearred in the place, and this is the characteristic peak of PMMA.
Embodiment 2
1, takes by weighing 0.018 gram AlCl
3Be dissolved in the deionized water, be mixed with solution A;
2, take by weighing the MgCl of 0.095 gram
2ZnCl with 0.008 gram
2Be dissolved in respectively in the deionized water, remix becomes solution B;
3, take by weighing 0.046 gram 5-cyanobiphenyl oxygen base oxethyl methyl-oxine is poured into after with anhydrous alcohol solution in the aqueous solution that contains 0.023 gram StNa, be mixed with mixed serum C;
4, under violent stirring; Simultaneously solution A and solution B are dropwise added among the mixed serum C, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to pH=13, in 60 ℃ of following ageings 12 hours; Suction filtration, water washing filter cake are to the pH=8 that filtrates; With suction filtration behind a small amount of soaked in absolute ethyl alcohol, the washing precipitate, filter cake obtains gold-tinted houghite sample in 105 ℃ of oven dry down.
5, get this gold-tinted houghite 0.1 gram; Add in pretreated TEB 3K of 0.9 gram and the 0.045 gram Potassium Persulphate; Fully soak and mix after 24 hours, place microwave, microwave frequency 2.45GHz; Polymerization time 3 minutes promptly gets exfoliated gold-tinted houghite/polymer nanocomposites.
Embodiment 3
1, takes by weighing 0.019 gram AlCl
3Be dissolved in the deionized water, be mixed with solution A;
2, take by weighing the MgCl of 0.14 gram
2ZnCl with 0.02 gram
2Be dissolved in respectively in the deionized water, remix becomes solution B;
3, take by weighing 0.071 gram 5-chloroethoxy methyl oxine and pour in the aqueous solution that contains 0.09 gram StNa after with anhydrous alcohol solution, be mixed with mixed serum C;
4, under violent stirring; Simultaneously solution A and solution B are dropwise added among the mixed serum C, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to pH=9, in 70 ℃ of following ageings 11 hours; Suction filtration, water washing filter cake are to the pH=7 that filtrates; With suction filtration behind a small amount of soaked in absolute ethyl alcohol, the washing precipitate, filter cake obtains gold-tinted houghite sample under 110 ℃.
5, get this gold-tinted houghite 0.1 gram; Add in pretreated vinylbenzene of 0.5 gram and the 0.025 gram BPO; Fully soak and mix after 24 hours, place microwave, microwave frequency 2.45GHz; Polymerization time 3 minutes promptly gets exfoliated gold-tinted houghite/polymer nanocomposites.
Embodiment 4
1, takes by weighing 0.039 gram AlCl
3Be dissolved in the deionized water, be mixed with solution A;
2, take by weighing the MgCl of 0.16 gram
2ZnCl with 0.02 gram
2Be dissolved in respectively in the deionized water, remix becomes solution B;
3, take by weighing 0.073 gram 5-ethoxyl methyl-oxine and pour in the aqueous solution that contains 0.064 gram StNa after with anhydrous alcohol solution, be mixed with mixed serum C;
4, under violent stirring; Simultaneously solution A and solution B are dropwise added among the mixed serum C, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to pH=10, in 70 ℃ of following ageings 10 hours; Suction filtration, water washing filter cake are to the pH=8 that filtrates; With suction filtration behind a small amount of soaked in absolute ethyl alcohol, the washing precipitate, filter cake obtains gold-tinted houghite sample under 105 ℃.
5, get this gold-tinted houghite 0.1 gram, add in pretreated aniline of 0.9 gram and the 0.045 gram ammonium persulphate, fully soak and mix after 24 hours; Place microwave; Microwave frequency 2.45GHz, polymerization time 3 minutes promptly gets exfoliated gold-tinted houghite/polymer nanocomposites.
Embodiment 5
1, takes by weighing 0.057 gram AlCl
3Be dissolved in the deionized water, be mixed with solution A;
2, take by weighing the MgCl of 0.14 gram
2ZnCl with 0.009 gram
2Be dissolved in respectively in the deionized water, remix becomes solution B;
3, take by weighing 0.034 gram 2-(2-hydroxystyrene based)-oxine and pour into after with anhydrous alcohol solution in the aqueous solution that contains 0.067 gram StNa, be mixed with mixed serum C;
4, under violent stirring; Simultaneously solution A and solution B are dropwise added among the mixed serum C, with 20% aqueous sodium hydroxide solution conditioned reaction mixed serum to pH=12, in 80 ℃ of following ageings 12 hours; Suction filtration, water washing filter cake are to the pH=7 that filtrates; With suction filtration behind a small amount of soaked in absolute ethyl alcohol, the washing precipitate, filter cake obtains gold-tinted houghite sample in 100 ℃ of oven dry down.
5, get this gold-tinted houghite 0.1 gram; Add in pretreated TEB 3K of 0.6 gram and the 0.03 gram Diisopropyl azodicarboxylate; Fully soak and mix after 24 hours, place microwave, microwave frequency 2.45GHz; Polymerization time 3 minutes promptly gets exfoliated gold-tinted houghite/polymer nanocomposites.
Claims (10)
1. the preparation method of an exfoliated gold-tinted houghite/polymer nanocomposites is characterized in that:
1) aluminum chloride is dissolved in the deionized water, is mixed with solution A;
Magnesium chloride and zinc chloride are dissolved in respectively in the deionized water, and remix becomes solution B;
Molten the mixing of part is mixed with mixed serum C in StNa;
2) under violent stirring or UW effect; Simultaneously mixed solution A and solution B are dropwise added among the mixed serum C, the conditioned reaction mixed serum is to pH=9～13, in 60～80 ℃ of following ageings 9～12 hours; Suction filtration, water washing filter cake are to pH=7～8 of filtrating eventually; Suction filtration behind the washing precipitate, filter cake was dried 2 hours down in 100～110 ℃, obtained the gold-tinted houghite of hyperfluorescence;
3) the gold-tinted houghite that will go up step preparation was soaked in pretreated polymer monomer and the initiator after 24 hours; Place microwave; Microwave frequency 2.45GHz, polymerization time 3 minutes promptly gets exfoliated gold-tinted houghite/polymer nanocomposites.
2. the preparation method of a kind of exfoliated gold-tinted houghite/polymer nanocomposites according to claim 1 is characterized in that described part is oxine or oxine verivate.
3. the preparation method of a kind of exfoliated gold-tinted houghite/polymer nanocomposites according to claim 1 is characterized in that described pretreated polymer monomer is meant TEB 3K, vinylbenzene or aniline.
4. the preparation method of a kind of exfoliated gold-tinted houghite/polymer nanocomposites according to claim 1 is characterized in that described initiator is meant Diisopropyl azodicarboxylate, Potassium Persulphate, BPO or ammonium persulphate.
5. the preparation method of a kind of exfoliated gold-tinted houghite/polymer nanocomposites according to claim 1 is characterized in that in the described solution B Mg
2+: Zn
2+Mol ratio be 1:0.04～0.13.
6. the preparation method of a kind of exfoliated gold-tinted houghite/polymer nanocomposites according to claim 1 is characterized in that the Mg in the described solution B
2+With the Al in the solution A
3+Mol ratio be 1:0.097～0.31.
7. the preparation method of a kind of exfoliated gold-tinted houghite/polymer nanocomposites according to claim 1 is characterized in that described part, with Zn in the solution B
2+Mol ratio be 1:2.
8. the preparation method of a kind of exfoliated gold-tinted houghite/polymer nanocomposites according to claim 1 is characterized in that the Mg in the solution B
2+With the mol ratio of StNa be 1:0.04～0.3.
9. the preparation method of a kind of exfoliated gold-tinted houghite/polymer nanocomposites according to claim 1 is characterized in that the mass ratio of gold-tinted Lei Shui Hua Shi ︰ polymer monomer is 1:5.5～19.
10. the preparation method of a kind of exfoliated gold-tinted houghite/polymer nanocomposites according to claim 1 is characterized in that described initiator, and its quality is 5% of a polymer monomer quality.
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Cited By (5)
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|---|---|---|---|---|
| CN103408682A (en) * | 2013-07-23 | 2013-11-27 | 福建师范大学 | White-light-type hydrotalcite nano composite material and application thereof for LED light source |
| CN103785430A (en) * | 2014-02-27 | 2014-05-14 | 常州大学 | Preparation method of bentonite lamella load silver phosphate modified by carbon fibers |
| CN103801341A (en) * | 2014-02-27 | 2014-05-21 | 常州大学 | Method for preparing carbon fiber modified hydrotalcite lamella loaded silver phosphate |
| CN106589219A (en) * | 2016-12-16 | 2017-04-26 | 咸阳师范学院 | Preparation method for fluorescent hydrotalcite/acrylic resin composite material |
| FR3048702A1 (en) * | 2016-03-14 | 2017-09-15 | Univ Blaise Pascal - Clermont Ii | MATERIAL COMPOSITE LUMINESCENT WITHOUT RARE EARTH |
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| CN101070415A (en) * | 2007-06-15 | 2007-11-14 | 浙江大学 | Polyvinyl chloride/nano hydrotalcite composite resin preparing method |
| CN101195741A (en) * | 2007-12-14 | 2008-06-11 | 福建师范大学 | Zincium containing hydrotalcite with strong fluoresce and method for producing the same |
| CN102618074A (en) * | 2012-02-24 | 2012-08-01 | 山东大学 | Thermal stabilization type ponceau 2R intercalation hydrotalcite dye and preparation method thereof |
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| CN101070415A (en) * | 2007-06-15 | 2007-11-14 | 浙江大学 | Polyvinyl chloride/nano hydrotalcite composite resin preparing method |
| CN101195741A (en) * | 2007-12-14 | 2008-06-11 | 福建师范大学 | Zincium containing hydrotalcite with strong fluoresce and method for producing the same |
| CN102618074A (en) * | 2012-02-24 | 2012-08-01 | 山东大学 | Thermal stabilization type ponceau 2R intercalation hydrotalcite dye and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103408682A (en) * | 2013-07-23 | 2013-11-27 | 福建师范大学 | White-light-type hydrotalcite nano composite material and application thereof for LED light source |
| CN103785430A (en) * | 2014-02-27 | 2014-05-14 | 常州大学 | Preparation method of bentonite lamella load silver phosphate modified by carbon fibers |
| CN103801341A (en) * | 2014-02-27 | 2014-05-21 | 常州大学 | Method for preparing carbon fiber modified hydrotalcite lamella loaded silver phosphate |
| CN103785430B (en) * | 2014-02-27 | 2015-06-24 | 常州大学 | Preparation method of bentonite lamella load silver phosphate modified by carbon fibers |
| CN103801341B (en) * | 2014-02-27 | 2015-06-24 | 常州大学 | Method for preparing carbon fiber modified hydrotalcite lamella loaded silver phosphate |
| FR3048702A1 (en) * | 2016-03-14 | 2017-09-15 | Univ Blaise Pascal - Clermont Ii | MATERIAL COMPOSITE LUMINESCENT WITHOUT RARE EARTH |
| WO2017158284A1 (en) * | 2016-03-14 | 2017-09-21 | Universite Blaise Pascal - Clermont Ii | Rare-earth-free luminescent composite material |
| CN106589219A (en) * | 2016-12-16 | 2017-04-26 | 咸阳师范学院 | Preparation method for fluorescent hydrotalcite/acrylic resin composite material |
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Application publication date: 20121128 |