CN115109586A - Preparation method of mechanoluminescence material - Google Patents
Preparation method of mechanoluminescence material Download PDFInfo
- Publication number
- CN115109586A CN115109586A CN202110301500.9A CN202110301500A CN115109586A CN 115109586 A CN115109586 A CN 115109586A CN 202110301500 A CN202110301500 A CN 202110301500A CN 115109586 A CN115109586 A CN 115109586A
- Authority
- CN
- China
- Prior art keywords
- source
- solution
- mechanoluminescence
- acid solution
- acidic solution
- 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
- 238000005166 mechanoluminescence Methods 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000003929 acidic solution Substances 0.000 claims abstract description 65
- 239000012670 alkaline solution Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims description 50
- 239000002253 acid Substances 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000001723 curing Methods 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 9
- 239000002861 polymer material Substances 0.000 claims description 9
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- -1 polydimethylsiloxane Polymers 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 229920001971 elastomer Polymers 0.000 claims description 6
- 239000000806 elastomer Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910001849 group 12 element Inorganic materials 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 5
- 238000000975 co-precipitation Methods 0.000 abstract description 4
- 239000012071 phase Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000000498 ball milling Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000002994 raw material Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 16
- 229910004860 CaZn Inorganic materials 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000004448 titration Methods 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 238000000227 grinding Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 229910001868 water Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910001437 manganese ion Inorganic materials 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000005457 ice water Substances 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/57—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing manganese or rhenium
- C09K11/572—Chalcogenides
- C09K11/574—Chalcogenides with zinc or cadmium
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The application discloses a preparation method of a mechanoluminescence material, wherein the mechanoluminescence material has the general formula: a. the (1‑x) QOS xM or AQ (1‑x) OS: xM; the method comprises at least the following steps: step 1, obtaining an acidic solution containing a source A, a source Q and a source M; obtaining an alkaline solution containing an S source; step 2, reacting the acidic solution with the alkaline solution to obtain a precursor; and 3, calcining the precursor to obtain the mechanoluminescence material. The method obtains the pure phase of the sample in a chemical coprecipitation mode, obtains better mechanoluminescence performance, and can avoid introducing impurity ions in the ball milling process by a solid phase method. The method can realize the control of the microscopic morphology of the material by adjusting the dropping modes of different acidic solutions and alkaline solutions.
Description
Technical Field
The application relates to a preparation method of a mechanoluminescence material, belonging to the field of luminescent materials.
Background
The visualization of material stress is applied in many aspects, such as electronic signature encryption, flaw detection of material parts, biomedical detection, and the like, and the application in the information storage direction is recently favored by many scholars. However, in the previous research work, many scholars adopt a strategy of synthesizing powder by a high-temperature solid phase method, but the method is single, the morphology of particles cannot be well regulated, and other impurities are introduced in the grinding or ball milling process, so that the application of the method in many aspects is limited.
Disclosure of Invention
According to one aspect of the application, a preparation method of the mechanoluminescence material is provided, the method adopts a chemical coprecipitation method to prepare a mechanoluminescence material pure product, and the introduction of impurity ions is avoided.
The preparation method of the mechanoluminescence material is characterized in that the mechanoluminescence material has a general formula shown in a formula I or a formula II:
A (1-x) QOS xM formula I
AQ (1-x) OS xM formula II
Wherein A is selected from alkaline earth metal elements;
q is selected from group IIB elements;
m is selected from any one of transition metal elements and lanthanide elements;
the value range of x is 0.0005-0.15;
the method comprises at least the following steps:
obtaining an alkaline solution containing an S source;
and 3, calcining the precursor to obtain the mechanoluminescence material.
Optionally, said A is selected from Ca 2+ 、Mg 2+ 、Ba 2+ 、Sr 2+ Any one of the above;
q is Zn 2+ ；
M is selected from Mn 2+ 、Cu 2+ 、Cr 3+ 、Ln 3+ Any one of them.
Optionally, the total concentration of cations in the acidic solution is 0.2-0.8 mol/L;
A. q, M molar ratio of elements is the stoichiometric ratio of each element in formula I or formula II; that is, in the preparation of the electroluminescent material, the source A, the source Q and the source M are weighed in the stoichiometric ratio shown in formula I or formula II.
The A source is selected from at least one of oxide, carbonate and nitrate of A;
the Q source is selected from at least one of oxide, carbonate and nitrate of Q;
the M source is selected from at least one of oxide, carbonate and nitrate of M.
Optionally, in step 1, obtaining an alkaline solution containing a source of S comprises:
dissolving an S source in an alkali solution to obtain the alkali solution containing the S source;
the S source is selected from NH 4 HSO 4 、(NH 4 ) 2 SO 3 ·H 2 O、SO 2 At least one of;
the alkali solution comprises NH 3 ·H 2 O。
Optionally, in the alkaline solution, the concentration of the S element is 0.5-3.2 mol/L.
The amount of the sulfur source is calculated according to the stoichiometric ratio in the general formula shown in the formula I or the formula II based on the molar content of the sulfur element, and in order to ensure that the reaction is sufficient, the ammonium sulfite or the ammonium bisulfate is weighed according to the proportion of excessive 20 percent in mass percentage in the implementation process.
Optionally, the step 2 includes:
titrating the acidic solution into the alkaline solution for reaction.
Optionally, the rate of titration is 8-12 ml/min.
The titration rate affects the growth of the precipitated particles, and a faster titration rate results in faster growth of the precipitated particles, which is detrimental to the uniformity of the precipitation.
Optionally, the step 2 further includes:
2.1 reacting the acidic solution with the alkaline solution to obtain a reaction solution containing a precipitate;
2.2 heating, cooling, filtering and drying the reaction solution containing the precipitate in sequence to obtain the precursor.
Optionally, in step 2.2, the heating conditions are:
heating to 65-90 ℃, and keeping the temperature for 1-5 h.
Specifically, the lower limit of the heating temperature can be selected from 65 deg.C, 68 deg.C, 70 deg.C, 30 deg.C, and 75 deg.C; the upper limit of the heating temperature can be independently selected from 78 deg.C, 80 deg.C, 82 deg.C, 85 deg.C, and 90 deg.C.
Specifically, the holding time can be independently selected from 1h, 2h, 3h, 4h, 5h, or any value between the two.
Optionally, in step 2.2, the cooling conditions are:
the cooling temperature is 0 ℃, and the cooling time is 10-30 min.
Specifically, the cooling time may be independently selected from 10min, 15min, 20min, 25min, 30min, or any value therebetween.
The heating mode can adopt direct heating, indirect heating and the like, and preferably adopts water bath heating; the cooling mode can select modes such as natural cooling, auxiliary cooling, preferably, adopts ice bath rapid cooling. The heating and cooling effects on the reaction liquid containing the precipitate are that the reaction is more sufficient through heating and heat preservation, the purity of the reaction product is improved, and meanwhile, the control on the shape of the precipitate is facilitated, so that the precipitate grows into complete particles; the product yield can be increased by rapid cooling.
The step 2.2 further comprises: washing the precipitate obtained by filtering;
the step 2.2 further comprises: and grinding the precursor.
Alternatively, in step 3, the calcination conditions are:
the calcining temperature is 600-850 ℃, and the calcining time is 2-5 h.
Specifically, the lower limit of the heating temperature can be independently selected from 600 deg.C, 620 deg.C, 650 deg.C, 680 deg.C, 700 deg.C; the upper limit of the heating temperature can be selected from 720 deg.C, 750 deg.C, 780 deg.C, 800 deg.C, 850 deg.C.
Specifically, the holding time may be independently selected from 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, or any value therebetween.
Alternatively, the calcination is carried out in the presence of a reducing atmosphere.
Optionally, the reducing atmosphere may adopt hydrogen, preferably, a mixed atmosphere of hydrogen and nitrogen may be adopted, and further preferably, the volume ratio of hydrogen to nitrogen in the mixed atmosphere is 0.05-0.2: 1.
optionally, in step 1, obtaining an acidic solution containing a source a, a source Q, and a source M, comprises:
adding a source A, a source Q and a source M into an acid solution to obtain an acid solution; or
Respectively adding a source A, a source Q and a source M into an acid solution to obtain an acid solution A, an acid solution Q and an acid solution M; or
Adding any two of the source A, the source Q and the source M into an acid solution to obtain an acid solution I; the remaining source of material is then added to the acid solution to obtain acid solution II.
Optionally, the acid solution is selected from any one of aqua regia and concentrated nitric acid solution.
Preferably, the mass percentage concentration of the concentrated nitric acid solution is 65-68 wt%.
Optionally, the step 2 includes:
sequentially adding the acidic solution of A, the acidic solution of Q and the acidic solution of M into the alkaline solution according to a certain sequence to react; or
And sequentially adding the acidic solution I and the acidic solution II into the alkaline solution according to a certain sequence to react.
The "certain order" means that the dropping order of different acidic solutions is firstly determined, and then the various acidic solutions are sequentially dropped into the alkaline solution.
By changing the adding sequence of the acid solutions containing different raw materials, the mechanoluminescence materials with different morphologies can be obtained, the core-shell structures with different coating directions are realized, and the samples with various layered structures can be realized by adding the acid solutions of various raw materials. For example, the core-shell structured mechanoluminescence material containing the element A, the element Q and the element M can be formed by dropping the acidic solution in the order of the acidic solution A, the acidic solution Q and the acidic solution M. The mixed acidic solution containing A, Q, M, on the other hand, does not have the above-described coating structure when added dropwise to a sulfur-containing alkaline solution.
Optionally, the method further comprises step 4;
and 4, mixing the mechanoluminescence material obtained in the step 3 with a high polymer material, and curing to obtain the mechanoluminescence elastomer.
Optionally, the polymer material is selected from any one of polydimethylsiloxane, polyurethane and polyethylene terephthalate.
Optionally, the mass ratio of the mechanoluminescence material to the polymer material is 1: 1.5 to 3.5.
Specifically, the mass ratio of the mechanoluminescence material to the polymer material may be independently selected from 1: 1.5, 1: 2. 1: 2.5, 1: 3. 1: 3.5, or any value in between.
The curing comprises adding a curing agent into a mixture of the mechanoluminescence material and the high polymer material, and the curing mode can be natural curing at normal temperature or heating curing. The skilled person can select different suitable curing methods to cure according to the actual situation. The selection and amount of the curing agent are routine for those skilled in the art, and those skilled in the art can select an appropriate curing agent and amount according to the polymer material and amount used.
In another embodiment of the present application, the method comprises at least the following steps:
firstly, obtaining an acidic solution containing an A source, a Q source and an M source;
obtaining an alkaline solution containing bicarbonate;
secondly, reacting the acidic solution with the alkaline solution to obtain a precursor A;
step three, mixing the precursor A and SO 2 Reacting to obtain a precursor B;
and fifthly, calcining the precursor B to obtain the mechanoluminescence material.
Optionally, step two includes:
reacting the acidic solution with the alkaline solution for precipitation, and filtering to obtain a precursor A;
optionally, step three includes: dispersing the precursor A in deionized water, and then introducing SO 2 And reacting until the pH value is 5.5-6.5 to obtain a precursor B.
The beneficial effects that this application can produce include:
1) the method obtains the pure phase of the sample in a chemical coprecipitation mode, obtains better mechanoluminescence performance, and can avoid introducing impurity ions in the ball milling process by a solid phase method.
2) According to the method, the titration rate of the acidic solution and the dripping sequence of different raw materials of the acidic solution are controlled, the particle size, the coating direction of particles and the like can be regulated, and the micro-morphology of the material can be controlled.
3) The method can obtain pure phase only by calcining the sample synthesized by the chemical coprecipitation method at the temperature of 600-850 ℃, and greatly reduces the calcining temperature compared with the traditional solid phase method in which the sample is calcined at the high temperature of 1100 ℃.
4) Compared with the traditional high-temperature solid phase method, the particle size of the mechanoluminescence material prepared by the preparation method is smaller.
Drawings
FIG. 1 is an X-ray diffraction spectrum of a sample obtained in embodiment 1-2 of the present application;
FIG. 2 is a photoluminescence spectrum of samples obtained by different manganese ion doping amounts at a wavelength of 200-550 nm in example 2 of the present application;
FIG. 3 is a photoluminescence spectrum at a wavelength of 350-700 nm of samples obtained by different manganese ion doping amounts in example 2 of the present application;
FIG. 4 is a graph showing luminescence properties of a sample obtained by doping manganese ions with a doping amount of 2% in example 2 of the present application under different pressure conditions;
FIG. 5 is an X-ray diffraction spectrum of a sample obtained by doping a manganese ion in an amount of 2% in examples 2 and 3 of the present application;
FIG. 6 is a scanning electron micrograph of a sample obtained in example 2 of the present application;
FIG. 7 is a scanning electron micrograph of a sample obtained in example 4 of the present application;
FIG. 8 shows the particle size distribution of the sample obtained in example 4 of the present application (FIG. a) and the sample obtained by the conventional high temperature solid phase method (FIG. b).
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials in the examples of the present application were purchased commercially, wherein CZOS-ICSD 245826 represents a standard sample; 01-076-3819CaZnOS represents a standard sample.
The analytical methods in the examples of the present application are as follows:
the composition of the material was analyzed by X-ray diffractometer (Bruker D8) (XRD).
Photoluminescence properties of the materials were analyzed using a fluorescence spectrometer (FL3-111, Horiba, France).
The morphological analysis of the material was performed using a field emission scanning electron microscope (Hitachi S-4800).
According to one embodiment of the present application, a method for preparing a mechanoluminescence material comprises the steps of:
Dissolving the raw materials in a conical flask by using the freshly prepared aqua regia to prepare an acidic solution with the pH of about 1.5, filtering the acidic solution into a beaker, and diluting the acidic solution with deionized water until the total concentration of cations is about 0.2-0.8 mol/L.
In this step, the raw material containing the target element may be separately prepared into an acidic solution to obtain an acidic solution of a, an acidic solution of Q, and an acidic solution of M; or mixing at least any two of the three raw materials containing the target element to prepare an acid solution I, and then adding at least one of the source A, the source Q and the source M which are different from the acid solution I into the acid solution to prepare an acid solution II; the three raw materials containing the target element can be added into the acid solution to obtain a mixed acid solution.
Taking deionized water and NH according to the proportion 3 ·H 2 O and sulfur-containing ammonium salt are put in a beaker, the concentration of sulfur element in the obtained alkaline solution is 1-4mol/L, and the pH value of the obtained alkaline solution is about 9.
And 4, carrying out reaction on the precursor at the temperature of 600-850 ℃ with 20% hydrogen by volume: calcining for 2-5 h under the condition of 80% nitrogen mixed gas to obtain the mechanoluminescence powder.
And 5, mixing the mechanoluminescence powder with Polydimethylsiloxane (PDMS) according to the weight ratio of 1: 1.5-3.5, and curing at normal temperature to obtain the mechanoluminescence elastomer.
In another embodiment of the present application, step 2, deionized water and NH are taken in proportion 3 ·H 2 O and NH 4 HCO 3 In a beaker, the concentration of sulfur element in the obtained alkaline solution is 1-4mol/L, and the pH of the obtained alkaline solution is about 9.
Example 1
Respectively weighing CaCO according to the stoichiometric ratio of CaZnOS 3 ZnO, all materials were dissolved in an erlenmeyer flask with aqua regia to produce an acidic solution having a pH of about 1.5, which was then filtered into a beaker and diluted to 800ml with deionized water to give a total cation concentration of about 0.8 mol/L.
Taking deionized water and NH according to the stoichiometric ratio of CaZnOS 3 ·H 2 O and NH 4 HSO 4 In a beaker, the concentration of elemental sulfur in the obtained alkaline solution was 4mol/L, the pH of the obtained alkaline solution was about 9, and the volume of the alkaline solution was 350 ml.
And 4, carrying out reaction on the precursor at the temperature of 750 ℃ with hydrogen with the volume ratio of 20 percent: calcining for 4 hours under the condition of 80% nitrogen mixed gas to obtain the mechanoluminescence powder. Designated sample F0.
And 5, mixing the mechanoluminescence powder with Polydimethylsiloxane (PDMS) according to the weight ratio of 1: 2, and curing at normal temperature to obtain the mechanoluminescence elastomer. Designated sample T0.
Example 2
Incorporation of Mn in a mechanoluminescence material 2+ ，Mn 2+ The theoretical equation for doping is CaZn (1-x) OS:xMn 2+ Wherein Mn is present in a molar percentage of the element 2+ The doping amount is 0.05-15%, namely x is more than or equal to 0.0005 and less than or equal to 0.15.
According to CaZn (1-x) And (3) OS: the stoichiometric ratio of xMn is respectively called CaCO 3 ZnO, MnO, all materials were dissolved in an erlenmeyer flask with aqua regia to prepare an acidic solution having a pH of about 1.5, which was then filtered into a beaker and diluted to 800ml with deionized water to a total cation concentration of about 0.8 mol/L.
According to CaZn (1-x) And OS: stoichiometric ratio of xMn, deionized water and NH are taken according to proportion 3 ·H 2 O and NH 4 HSO 4 In a beaker, the concentration of elemental sulfur in the resulting alkali solution was 4mol/L, the pH of the resulting alkali solution was about 9, and the volume of the alkali solution was 350 ml.
And 4, carrying out reaction on the precursor at the temperature of 750 ℃ with hydrogen with the volume ratio of 20 percent: calcining for 4 hours under the condition of 80% nitrogen mixed gas to obtain the mechanoluminescence powder.
And 5, mixing the mechanoluminescence powder with Polydimethylsiloxane (PDMS) according to the weight ratio of 1: 2, and curing at normal temperature to obtain the mechanoluminescence elastomer.
The technological parameters of the obtained mechanoluminescence material are shown in Table 1.
Example 3
The preparation process of the mechanoluminescence material in the present example is substantially the same as that in example 2, except that: mn 2+ The doping amount of (A) is 2%;
in step 3, the alkaline solution is added dropwise to the acidic solution. The resulting mechanoluminescence powder was designated as sample F13 and the mechanoluminescence elastomer was designated as sample T13.
Example 4
According to Zn 0.98 SMn 0.02 Respectively weighing ZnO and Mn (NO) according to the stoichiometric ratio 3 ) 2 Dissolving all raw materials in a conical flask by using aqua regia to prepare an acidic solution I with the pH value of about 1.5; diluted to 800ml with deionized water to give a total cation concentration of about 0.8 mol/L.
According to CaZn 0.98 OSMn 0.02 The CaO, the ZnO and the MnO are respectively weighed according to the stoichiometric ratio, all the raw materials are dissolved in a conical flask by using aqua regia, and the pH value of the prepared acid solution II is about 1.5; diluted to 800ml with deionized water to give a total cation concentration of about 0.8 mol/L.
The acidic solution I, II was separately filtered into a beaker and diluted with deionized water to a total cation concentration of 0.8mol/L in the acidic solution I, II.
According to CaZn 0.98 OSMn 0.02 n, deionized water and NH are taken according to the proportion 3 ·H 2 O and NH 4 HSO 4 In a beaker, the concentration of elemental sulfur in the obtained alkaline solution was 4mol/L, the pH of the obtained alkaline solution was about 9, and the volume of the alkaline solution was 350 ml.
And 4, carrying out reaction on the precursor at the temperature of 600 ℃ with hydrogen with the volume ratio of 20 percent: calcining for 4 hours under the condition of 80% nitrogen mixed gas to obtain the mechanoluminescence powder. Designated sample F14.
Example 5
According to CaZn 0.98 OSMn 0.02 Are respectively called CaCO 3 、ZnO、MnCO 3 Dissolving all raw materials in a conical flask by using aqua regia to prepare an acidic solution with the pH of about 1.5; diluted to 1000ml with deionized water and having a total cation concentration of about 0.8 mol/L.
According to CaZn 0.98 OSMn 0.02 The deionized water, NH 3. H2O and NH are taken according to the proportion 4 HCO 3 The bicarbonate concentration of the resulting alkaline solution was 4mol/L in a beaker, and the resulting alkaline solution had a pH of about 9 and a volume of about 400 ml.
And 4, carrying out reaction on the precursor at the temperature of 750 ℃ with hydrogen with the volume ratio of 20 percent: calcining for 4 hours under the condition of 80% nitrogen mixed gas to obtain the mechanoluminescence powder. Designated sample F15.
Example 6
The samples obtained in examples 1 to 4 were subjected to characterization and performance tests.
When the powder samples are subjected to X-ray diffraction spectrum analysis and compared with the standard, typically, taking samples F0, F5, F6, F8 and F10 as examples, as shown in FIG. 1, it can be seen that the mechanoluminescence material obtained after calcination in the present application is substantially pure phase, and only CaSO having no influence on luminescence intensity and peak position is generated 4 The impurities of (1). Only manganese ions are generated when the doping concentration of manganese ions is high, because the manganese ions occupy zinc ion sites when weighed according to the stoichiometric ratio, the theoretical calculation amount of the zinc ions is reduced, and finally the formation of calcium sulfate is caused.
The powder samples F0-F10 were analyzed for photoluminescence, and as shown in FIGS. 2 and 3, the excitation peak of the mechanoluminescence powder obtained in the present application was 280nm, the emission peak positions were 536nm and 610nm, and the emission peaks at 536nm and 610nm both consisted of Mn 2+ Is/are as follows 4 T 1 (4G)→ 6 A 1 (6S) energy level transition.
For sample T4 (CaZn) 0.98 OSMn 0.02 ) The mechanoluminescence test was carried out by processing a sample T4 into a cylinder having a diameter of 25mm and a height of 15mm and measuring the luminescence intensity under different pressure conditions. As shown in fig. 4, different amounts of pressure are applied to the material and the intensity of the force luminescence increases with increasing pressure applied to the sample.
Comparing the purities of samples F4 and F13 obtained in different dropping order at the same calcination temperature, the results are shown in FIG. 5, which uses CaZn obtained by titrating an acidic solution into an alkaline solution (saline-alkali solution) 0.98 OSMn 0.02 The sample was purer than that obtained by titration with an alkaline solution to an acidic solution (base salt).
For sample F4 (CaZn) 0.98 OSMn 0.02 ) Sample F14 (CaZn) 0.98 OSMn 0.02 ) When the scanning electron microscope analysis is performed, as shown in fig. 6 and 7, it can be seen that the microscopic morphology of the sample F4 powder is integrated, no core-shell structure is formed, and Zn is formed on the microscopic surface of the sample F14 powder 0.98 SMn 0.02 And CaZn 0.98 OSMn 0.02 Make up the bagA laminated core-shell structure.
CaZn synthesized by adopting traditional high-temperature solid-phase method 0.98 OSMn 0.02 The specific method comprises the following steps: raw materials of calcium carbonate, zinc sulfide and manganese carbonate are weighed according to a stoichiometric ratio, and then are subjected to dry grinding, namely, direct grinding in a mortar without adding any reagent such as absolute ethyl alcohol, wherein the grinding time is 1 hour. And (3) placing the ground sample in a nitrogen protective atmosphere, controlling the flow rate of nitrogen to be 250ml/min and the heating rate to be 10 ℃/min, heating to 1100 ℃, and preserving heat for 3h to obtain a powder sample.
Sample F4 and CaZn synthesized by conventional high temperature solid phase method 0.98 OSMn 0.02 As a result of analyzing the particle size of the sample by particle size detection, as shown in FIG. 8, the average particle size of the sample F4 obtained by the liquid phase method of the present application is about 1.43 μm (shown in FIG. 8 a), while the average particle size of the sample obtained by the conventional high temperature solid phase synthesis method is about 5.04 μm, which shows that the particle size of the sample obtained by the method of the present application is significantly reduced.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A method for preparing a mechanoluminescence material, wherein the mechanoluminescence material has the general formula shown in formula I or formula II:
A (1-x) QOS xM formula I
AQ (1-x) OS xM formula II
Wherein A is selected from alkaline earth elements;
q is selected from group IIB elements;
m is selected from any one of transition metal elements and lanthanide elements;
the value range of x is 0.0005-0.15;
the method comprises at least the following steps:
step 1, obtaining an acidic solution containing a source A, a source Q and a source M;
obtaining an alkaline solution containing an S source;
step 2, reacting the acidic solution with the alkaline solution to obtain a precursor;
and 3, calcining the precursor to obtain the mechanoluminescence material.
2. The method for preparing a mechanoluminescence material according to claim 1, wherein the total concentration of cations in the acidic solution is 0.2 to 0.8 mol/L;
A. q, M molar ratio of elements is the stoichiometric ratio of each element in formula I or formula II;
the A source is selected from at least one of oxide, carbonate and nitrate of A;
the Q source is selected from at least one of oxide, carbonate and nitrate of Q;
the M source is selected from at least one of oxide, carbonate and nitrate of M.
3. The method for preparing a mechanoluminescence material according to claim 1, wherein in the step 1, an alkaline solution containing a source of S is obtained, and comprises:
dissolving an S source in an alkali solution to obtain the alkali solution containing the S source;
the S source is selected from NH 4 HSO 4 、(NH 4 ) 2 SO 3 ·H 2 O、SO 2 At least one of;
the alkali solution comprises NH 3 ·H 2 O。
4. The method for preparing a mechanoluminescence material according to claim 1, wherein the concentration of the S element in the alkaline solution is 0.5 to 3.2 mol/L.
5. The method for preparing a mechanoluminescence material according to claim 1, wherein the step 2 comprises:
titrating the acidic solution into the alkaline solution for reaction.
6. The method for preparing a mechanoluminescence material according to claim 1, wherein the step 2 further comprises:
2.1 reacting the acidic solution with the alkaline solution to obtain a reaction solution containing a precipitate;
and 2.2, heating, cooling, filtering and drying the reaction solution containing the precipitate in sequence to obtain the precursor.
7. The method for preparing a mechanoluminescence material according to claim 6, wherein in the step 2.2, the heating conditions are:
heating to 65-90 ℃, and keeping the temperature for 1-5 h;
preferably, in step 2.2, the cooling conditions are:
the cooling temperature is 0 ℃, and the cooling time is 10-30 min.
8. The method for preparing a mechanoluminescence material according to claim 1, wherein in step 3, the calcination conditions are:
the calcination temperature is 600-850 ℃, and the calcination time is 2-5 h;
preferably, the calcination is carried out in the presence of a reducing atmosphere.
9. The method for preparing the mechanoluminescence material according to claim 1, wherein in the step 1, an acidic solution containing a source a, a source Q and a source M is obtained by:
adding a source A, a source Q and a source M into an acid solution to obtain an acid solution; or
Respectively adding the source A, the source Q and the source M into an acid solution to obtain an acid solution A, an acid solution Q and an acid solution M; or
Adding at least any two of the source A, the source Q and the source M into an acid solution to obtain an acid solution I; then adding at least one of a source A, a source Q and a source M which are different from the acid solution I into the acid solution to obtain an acid solution II;
preferably, the acid solution is selected from any one of aqua regia and concentrated nitric acid solution;
preferably, the step 2 includes:
sequentially adding the acidic solution A, the acidic solution Q and the acidic solution M into the alkaline solution according to a certain sequence for reaction; or
And sequentially adding the acidic solution I and the acidic solution II into the alkaline solution according to a certain sequence to react.
10. A method for producing a mechanoluminescence material according to any one of claims 1 to 9, characterized by further comprising the steps of 4;
step 4, mixing and curing the mechanoluminescence material obtained in the step 3 and a high polymer material to obtain a mechanoluminescence elastomer;
preferably, the polymer material is selected from any one of polydimethylsiloxane, polyurethane and polyethylene terephthalate;
preferably, the mass ratio of the mechanoluminescence material to the polymer material is 1: 1.5 to 3.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110301500.9A CN115109586B (en) | 2021-03-22 | 2021-03-22 | Preparation method of mechanoluminescence material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110301500.9A CN115109586B (en) | 2021-03-22 | 2021-03-22 | Preparation method of mechanoluminescence material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115109586A true CN115109586A (en) | 2022-09-27 |
| CN115109586B CN115109586B (en) | 2024-05-31 |
Family
ID=83324077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110301500.9A Active CN115109586B (en) | 2021-03-22 | 2021-03-22 | Preparation method of mechanoluminescence material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115109586B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618263A (en) * | 2012-03-16 | 2012-08-01 | 武汉工程大学 | Preparation method for silicate luminescent material |
| US20130075657A1 (en) * | 2010-06-18 | 2013-03-28 | Ocean's King Lighting Science & Technology Co., Ltd. | Halogen silicate luminescent material and the preparation method and application thereof |
| US20130075661A1 (en) * | 2010-06-13 | 2013-03-28 | Ocean's King Lighting Science & Technology Co., Ltd. | Silicate luminous material and preparation method thereof |
| CN103936420A (en) * | 2014-04-17 | 2014-07-23 | 中国科学院宁波材料技术与工程研究所 | Method for preparing garnet phase scintillator powder deviated from stoichiometric ratio through Chemical coprecipitation method |
| CN107163942A (en) * | 2017-05-12 | 2017-09-15 | 华南理工大学 | Small particle cerium dropped yttrium aluminum garnet fluorescent material and method and application prepared by a kind of coprecipitation |
| CN110229657A (en) * | 2019-04-26 | 2019-09-13 | 深圳科尔新材料科技有限公司 | The preparation method of long afterglow mechanoluminescence material |
| CN110980749A (en) * | 2019-12-31 | 2020-04-10 | 中南大学 | Ytterbium disilicate powder material and application |
| CN112029502A (en) * | 2020-08-04 | 2020-12-04 | 盐城工学院 | Lanthanum silicate luminescent powder material with apatite structure and preparation method and application thereof |
-
2021
- 2021-03-22 CN CN202110301500.9A patent/CN115109586B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130075661A1 (en) * | 2010-06-13 | 2013-03-28 | Ocean's King Lighting Science & Technology Co., Ltd. | Silicate luminous material and preparation method thereof |
| US20130075657A1 (en) * | 2010-06-18 | 2013-03-28 | Ocean's King Lighting Science & Technology Co., Ltd. | Halogen silicate luminescent material and the preparation method and application thereof |
| CN102618263A (en) * | 2012-03-16 | 2012-08-01 | 武汉工程大学 | Preparation method for silicate luminescent material |
| CN103936420A (en) * | 2014-04-17 | 2014-07-23 | 中国科学院宁波材料技术与工程研究所 | Method for preparing garnet phase scintillator powder deviated from stoichiometric ratio through Chemical coprecipitation method |
| CN107163942A (en) * | 2017-05-12 | 2017-09-15 | 华南理工大学 | Small particle cerium dropped yttrium aluminum garnet fluorescent material and method and application prepared by a kind of coprecipitation |
| CN110229657A (en) * | 2019-04-26 | 2019-09-13 | 深圳科尔新材料科技有限公司 | The preparation method of long afterglow mechanoluminescence material |
| CN110980749A (en) * | 2019-12-31 | 2020-04-10 | 中南大学 | Ytterbium disilicate powder material and application |
| CN112029502A (en) * | 2020-08-04 | 2020-12-04 | 盐城工学院 | Lanthanum silicate luminescent powder material with apatite structure and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZIHAN XU等: "Two-Step Synthesis and Surface Modification of CaZnOS:Mn2+ Phosphors and the Fabrication of a Luminescent Poly(dimethylsiloxane) Film", INORGANIC CHEMISTRY, vol. 57, pages 1670 - 1675 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115109586B (en) | 2024-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE112005000930B4 (en) | α-SiAlON powder and process for the preparation thereof | |
| EP3245159B1 (en) | A process for converting natural calcium carbonate into precipitated calcium carbonate | |
| US9725330B2 (en) | Production of high purity precipitated calcium carbonate | |
| EP3738926B1 (en) | Preparation method for nanoprecipitated calcium carbonate having core-shell structure | |
| CN1641077A (en) | Method for preparing aragonite type calcium carbonate whisker | |
| CN106495200A (en) | A kind of anhydrous slufuric acid salt form rare earth layered hydroxide and preparation method thereof | |
| CN111057399B (en) | Preparation method of rare earth doped clay mineral-based bismuth yellow hybrid pigment with adjustable fluorescence and color | |
| Yin et al. | Preparation of crystalline rare earth carbonates with large particle size from the lixivium of weathered crust elution-deposited rare earth ores | |
| JP2014058435A (en) | Low bet spherical manganese tetraoxide and its production method | |
| CN115109586B (en) | Preparation method of mechanoluminescence material | |
| JP3913821B2 (en) | Method for producing cubic calcium carbonate with controlled particle size | |
| KR19990086224A (en) | Method of preparing calcium carbonate | |
| CN112299491B (en) | Method for synthesizing ferrous ammonium sulfite | |
| JP5081438B2 (en) | Method for producing magnesium oxide | |
| CN109777422B (en) | Blue fluorescent powder suitable for purple light excitation, preparation method thereof and light-emitting device | |
| JP2001270713A (en) | Method for producing calcium carbonate having aragonite crystal system | |
| CN111944350B (en) | YAG Ce-based warm white fluorescent automobile paint and preparation method thereof | |
| CN106517294B (en) | Process for producing metal oxide | |
| US20230338919A1 (en) | Sorbent compositions and methods of manufacture for use in concentrating lithium from brines | |
| Chen et al. | Morphology control and luminescent properties of Eu/Tb-doped calcium carbonate nanoparticles using natural limestone | |
| Kong et al. | Synthesis and luminescence properties of terbium-doped lanthanum oxychloride nanostructures | |
| CN105776331A (en) | Self sacrificing template synthesis method for preparation of rare earth vanadate with LRH as template | |
| CN112777643A (en) | Mg-doped modified lithium ion sieve and preparation method thereof | |
| KR101656035B1 (en) | A method for the synthesis of precipitated calcium carbonate from dolomite kiln dust | |
| JP2002235295A (en) | Method for producing calcium carbonate whisker |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |