CN115109586B - Preparation method of mechanoluminescence material - Google Patents
Preparation method of mechanoluminescence material Download PDFInfo
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- CN115109586B CN115109586B CN202110301500.9A CN202110301500A CN115109586B CN 115109586 B CN115109586 B CN 115109586B CN 202110301500 A CN202110301500 A CN 202110301500A CN 115109586 B CN115109586 B CN 115109586B
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- 238000005166 mechanoluminescence Methods 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 78
- 239000002253 acid Substances 0.000 claims abstract description 58
- 239000012670 alkaline solution Substances 0.000 claims abstract description 45
- 239000003929 acidic solution Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 150000001768 cations Chemical class 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
- 239000002861 polymer material Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000203 mixture Substances 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
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052784 alkaline earth metal 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
- 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
- 150000002500 ions Chemical class 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound 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 18
- 239000000843 powder Substances 0.000 description 15
- 229910004860 CaZn Inorganic materials 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 238000004448 titration Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 238000000227 grinding Methods 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 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
- 238000004458 analytical method Methods 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 238000001556 precipitation Methods 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
- 238000007873 sieving Methods 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 4
- 229910001437 manganese ion Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 230000000694 effects Effects 0.000 description 2
- 159000000011 group IA salts Chemical class 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 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
- 239000013049 sediment Substances 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 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
- 239000005083 Zinc sulfide Substances 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 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
- 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009837 dry grinding Methods 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
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 238000005303 weighing 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
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, which has the following general formula: a (1‑x) QOS: xM or AQ (1‑x) OS: xM; the method at least comprises the following steps: step 1, obtaining an acid solution containing an A source, a Q source and an M source; obtaining an alkaline solution containing an S source; step 2, reacting the acidic solution with the alkaline solution to obtain a precursor; and step 3, calcining the precursor to obtain the mechanoluminescence material. The application obtains the pure phase of the sample by chemical coprecipitation, 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 dripping mode of different acidic solutions and alkaline solutions.
Description
Technical Field
The application relates to a preparation method of a mechanoluminescence material, and belongs to the field of luminescent materials.
Background
Visualization of material stress has applications in many ways, such as electronic signature encryption, flaw detection of material parts, biomedical detection, etc., and applications in information storage have recently been favored by many students. However, in the previous research work, a high-temperature solid phase method is adopted by a plurality of scholars, but the method is relatively single, the morphology of particles cannot be well regulated and controlled, and other impurities are introduced in the grinding or ball milling process, so that the application of the method in various aspects is limited.
Disclosure of Invention
According to one aspect of the application, a method for preparing a mechanoluminescence material is provided, wherein the method adopts a chemical coprecipitation method to prepare a pure product of the mechanoluminescence material, 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 type I
AQ (1-x) OS xM II
Wherein A is selected from alkaline earth metal elements;
Q is selected from IIB group elements;
m is selected from any one of transition metal element and lanthanide;
The value range of x is 0.0005-0.15;
the method at least comprises the following steps:
step 1, obtaining an acid solution containing an A source, a Q source and an M source;
obtaining an alkaline solution containing an S source;
Step 2, reacting the acidic solution with the alkaline solution to obtain a precursor;
and step 3, calcining the precursor to obtain the mechanoluminescence material.
Optionally, the a is selected from any one of Ca 2+、Mg2+、Ba2+、Sr2+;
Q is Zn 2+;
and M is selected from any one of Mn 2+、Cu2+、Cr3+、Ln3+.
Optionally, the total concentration of cations in the acidic solution is 0.2-0.8 mol/L;
A. the molar concentration ratio of Q, M elements is the stoichiometric ratio of each element in the formula I or the formula II; namely, when preparing the mechanoluminescence material, the A source, the Q source and the M source are weighed according to the stoichiometric ratio shown in the formula I or the 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 an oxide, a carbonate and a nitrate of M.
Optionally, in step 1, obtaining an alkaline solution containing an S source, comprising:
Dissolving an S source in an alkali solution to obtain an alkali solution containing the S source;
The S source is selected from at least one of NH 4HSO4、(NH4)2SO3·H2O、SO2;
the alkaline solution comprises NH 3·H2 O.
Optionally, the concentration of the S element in the alkaline solution 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 by the molar content of sulfur element, and in order to fully react, the application weighs ammonium sulfite or ammonium bisulfate according to the proportion of 20 percent by mass in the implementation process.
Optionally, the step 2 includes:
titrating the acidic solution into the alkaline solution for reaction.
Optionally, the titration rate 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 precipitation.
Optionally, the step 2 further includes:
2.1, reacting the acidic solution with the alkaline solution to obtain a reaction solution containing precipitate;
And 2.2, heating, cooling, filtering and drying the reaction liquid containing the precipitate in sequence to obtain the precursor.
Optionally, in step 2.2, the heating condition is:
Heating to 65-90 deg.c for 1-5 hr.
Specifically, the lower heating temperature limit may be independently selected from 65 ℃, 68 ℃, 70 ℃,30 ℃, 75 ℃; the upper limit of the heating temperature can be independently selected from 78 ℃, 80 ℃, 82 ℃, 85 ℃ and 90 ℃.
Specifically, the incubation time may be independently selected from 1h, 2h, 3h, 4h, 5h, or any value between the two values.
Optionally, in step 2.2, the cooling condition is:
Cooling to 0 deg.c for 10-30 min.
Specifically, the cooling time may be independently selected from 10min, 15min, 20min, 25min, 30min, or any value between the two values.
The heating mode can be direct heating, indirect heating and the like, and preferably, water bath heating is adopted; the cooling mode can be natural cooling, auxiliary cooling and the like, and preferably, ice bath rapid cooling is adopted. The heating and cooling of the reaction liquid containing the precipitate has the effects that the reaction is more sufficient by heating and heat preservation, the purity of the reaction product is improved, and the control of the morphology of the precipitate is facilitated, so that the precipitate grows into complete particles; the product yield can be improved by rapid cooling.
The step 2.2 further comprises: washing the precipitate obtained by filtration;
The step 2.2 further comprises: and grinding the precursor.
Optionally, in step 3, the calcining conditions are:
The calcination temperature is 600-850 ℃ and the calcination time is 2-5 h.
Specifically, the lower heating temperature limit may be independently selected from 600 ℃, 620 ℃, 650 ℃, 680 ℃, 700 ℃; the upper limit of the heating temperature can be independently selected from 720 ℃, 750 ℃, 780 ℃, 800 ℃ and 850 ℃.
Specifically, the incubation time may be independently selected from 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, or any value therebetween.
Optionally, the calcining is performed in the presence of a reducing atmosphere.
Optionally, the reducing atmosphere may be hydrogen, preferably, a mixed atmosphere of hydrogen and nitrogen, 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 an a source, a Q source, and an M source, including:
Adding a source A, a source Q and a source M into an acid solution to obtain the acid solution; or (b)
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 (b)
Adding any two of a source A, a source Q and a 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 acid solution of A, the acid solution of Q and the acid solution of M into the alkaline solution according to a certain sequence to react; or (b)
And adding the acid solution I and the acid solution II into the alkaline solution in sequence according to a certain sequence to perform a reaction.
The term "certain order" means that the order of adding the different acidic solutions is first determined, and then the various acidic solutions are sequentially added into the alkaline solution.
According to the application, by changing the addition 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 lamellar structures can be realized by adding the acid solutions with various raw materials. For example, the acidic solution A, the acidic solution Q and the acidic solution M are added dropwise in sequence, so that the core-shell structure mechanoluminescence material containing the element A, the element Q and the element M can be formed from inside to outside. The mixed acidic solution containing A, Q, M was added dropwise to the alkaline solution containing sulfur, and the coating structure was not provided.
Optionally, the method further comprises step 4;
and step 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 between the two values.
The curing comprises adding a curing agent into a mixture of the mechanoluminescence material and the polymer material, wherein the curing mode can be natural curing at normal temperature or heating curing. The person skilled in the art can choose different suitable curing modes for curing according to the actual situation. The selection and amount of curing agent is a routine choice for those skilled in the art, and those skilled in the art can select the appropriate curing agent and amount depending on the polymeric material and amount used.
In another embodiment of the present application, the method comprises at least the steps of:
①, obtaining an acid solution containing an A source, a Q source and an M source;
obtaining an alkaline solution containing bicarbonate;
Step ②, reacting the acidic solution with the alkaline solution to obtain a precursor A;
③, reacting the precursor A with SO 2 to obtain a precursor B;
And ⑤, calcining the precursor B to obtain the mechanoluminescence material.
Optionally, step ② includes:
reacting and precipitating the acidic solution with the alkaline solution, and filtering to obtain a precursor A;
optionally, step ③ includes: dispersing the precursor A in deionized water, and then introducing SO 2 to react until the pH is 5.5-6.5, SO as to obtain a precursor B.
The application has the beneficial effects that:
1) The application obtains the pure phase of the sample by chemical coprecipitation, obtains better mechanoluminescence performance, and can avoid introducing impurity ions in the ball milling process by a solid phase method.
2) The application can realize the regulation and control of particle size, particle coating direction and the like by controlling the titration rate of the acid solution and the dripping sequence of the acid solutions of different raw materials, thereby realizing the control of the microscopic morphology of the material.
3) The application can obtain pure phase by calcining the sample synthesized by the chemical coprecipitation method at 600-850 ℃, and compared with the traditional solid phase method sample, the calcining at 1100 ℃ is needed, and the calcining temperature is greatly reduced by the method.
4) Compared with the traditional high-temperature solid phase method, the particle size of the mechanoluminescence material obtained 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 shows photoluminescence spectra of samples obtained in example 2 of the present application at wavelengths of 200-550 nm;
FIG. 3 shows photoluminescence spectra of samples obtained in example 2 of the present application at wavelengths of 350-700 nm with different manganese ion doping amounts;
FIG. 4 is a graph showing the luminescence properties of samples obtained with 2% doping amount of Mn ions in example 2 under different pressure conditions;
FIG. 5 is an X-ray diffraction spectrum of a sample obtained by 2% doping amount of manganese ions in examples 2 and 3 of the present application;
FIG. 6 is a scanning electron microscope image of a sample obtained in example 2 of the present application;
FIG. 7 is a scanning electron microscope image 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 (FIG. a) according to the present application and the sample obtained in the conventional high temperature solid phase method (FIG. b).
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, the starting materials in the examples of the present application were all purchased commercially, with CZOS-ICSD245309 representing a standard sample; 01-076-3819CaZnOS represents a standard sample.
The analysis method in the embodiment of the application is as follows:
the composition analysis of the material was performed using an X-ray diffractometer (Bruker D8) (XRD).
Photoluminescence performance analysis of the material was performed using a fluorescence spectrometer (FL 3-111, horiba, france).
Topography 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:
Step1, preparing an acidic solution of raw materials
The raw materials are dissolved in an conical flask by using the prepared aqua regia, the pH value of the prepared acidic solution is about 1.5, then the acidic solution is filtered into a beaker, and the acidic solution is diluted to the total concentration of cations of about 0.2-0.8 mol/L by using deionized water.
In the step, raw materials containing target elements can be independently prepared into an acid solution to obtain an acid solution A, an acid solution Q and an acid solution M; or mixing at least two of the three raw materials containing target elements to obtain an acidic solution I, and adding at least one of an A source, a Q source and an M source which are different from the composition of the acidic solution I into an acid solution to prepare an acidic solution II; three raw materials containing target elements can be added into the acid solution to obtain mixed acid solution.
Step 2, preparing alkali solution
Deionized water, NH 3·H2 O and ammonium sulfate salt are taken in a beaker according to a proportion, the concentration of sulfur element in the obtained alkali solution is 1-4mol/L, and the pH value of the obtained alkali solution is about 9.
Step 3, titrating the acid solution obtained in the step 1 into an alkali solution according to the speed of 8-12 ml/min, and stirring continuously in the titration process; after the precipitation is finished, heating to 65-90 ℃ in water bath, preserving heat and purifying for 1-5 hours, and keeping the magnetic stirring rate unchanged during the period; transferring the conical flask to ice water bath, rapidly cooling to 0 ℃ after 10-30min, washing and filtering with 5L of deionized water, drying, grinding for 10-20min, and sieving to obtain a white precursor.
Step 4, the precursor is subjected to hydrogen gas with the volume ratio of 20% at 600-850 ℃: calcining for 2-5 h under the condition of 80% nitrogen mixed gas to obtain the mechanoluminescence powder.
Step 5, mixing the mechanoluminescence powder with Polydimethylsiloxane (PDMS) according to the following formula 1: mixing the components according to a mass ratio of 1.5-3.5, and curing the mixture at normal temperature to obtain the mechanoluminescence elastomer.
In another embodiment of the present application, step 2, deionized water, NH 3·H2 O and NH 4HCO3 are taken in a beaker in proportion to obtain an alkaline solution having a concentration of elemental sulfur of 1-4mol/L and a pH of about 9.
Step 3, titrating the acid solution obtained in the step 1 into an alkali solution according to the speed of 8-12 ml/min, and stirring continuously in the titration process; after the precipitation is finished, the precipitate is filtered, then transferred to a conical flask, added with deionized water and stirred for dispersion. Introducing SO 2 gas into a conical flask containing sediment, and stopping introducing the gas when the pH value of the mixed solution in the conical flask is 5.5-6.5. Heating in water bath to 65-90 deg.c, maintaining the temperature and purifying for 1-5 hr while maintaining the magnetic stirring speed unchanged; transferring the conical flask to ice water bath, rapidly cooling to 0 ℃ after 10-30min, washing and filtering with 5L of deionized water, drying, grinding for 10-20min, and sieving to obtain a white precursor.
Example 1
Step1, preparing an acidic solution of raw materials
CaCO 3 and ZnO are weighed according to the stoichiometric ratio of CaZnOS, all raw materials are dissolved in an conical flask by aqua regia, the pH of the prepared acid solution is about 1.5, then the acid solution is filtered into a beaker, and the acid solution is diluted to 800ml by deionized water, so that the total concentration of cations is about 0.8mol/L.
Step2, preparing alkaline solution
Deionized water, NH 3·H2 O and NH 4HSO4 are proportionally taken according to the stoichiometric ratio of CaZnOS in a beaker, the concentration of sulfur element in the obtained alkali solution is 4mol/L, the pH of the obtained alkaline solution is about 9, and the volume of the alkaline solution is 350ml.
Step 3, titrating the acid solution obtained in the step 1 into the alkaline solution at a speed of 10ml/min, and continuously stirring in the titration process at a stirring speed of 500rpm; after the precipitation is finished, heating the reaction system to 90 ℃ in a water bath, preserving heat and purifying for 2 hours, and keeping the magnetic stirring rate unchanged during the period; transferring the conical flask to an ice-water bath, rapidly cooling to 0 ℃ after 30min, washing and filtering with 5L of deionized water, drying, grinding for 20min, and sieving with a 120-mesh sieve to obtain a white precursor.
Step 4, the precursor is subjected to hydrogen gas with the volume ratio of 20% at 750 ℃): calcining for 4 hours under the condition of 80% nitrogen mixed gas to obtain the mechanoluminescence powder. And is designated as sample F0.
Step 5, mixing the mechanoluminescence powder with Polydimethylsiloxane (PDMS) according to the following formula 1:2, and curing the mixture at normal temperature to obtain the mechanoluminescence elastomer. And is designated as sample T0.
Example 2
The theoretical equation of Mn 2+,Mn2+ doping in the mechanoluminescence material is CaZn (1-x)OS:xMn2+, wherein the doping amount of Mn 2+ is 0.05% -15% in terms of mole percent of elements, namely 0.0005.ltoreq.x.ltoreq.0.15.
Step1, preparing an acidic solution of raw materials
According to CaZn (1-x) OS: the stoichiometric ratios of xMn were weighed CaCO 3, znO, mnO, respectively, all raw materials were dissolved in an erlenmeyer flask with aqua regia to prepare an acidic solution having a pH of about 1.5, and the acidic solution was filtered into a beaker and diluted to 800ml with deionized water to give a total cation concentration of about 0.8mol/L.
Step2, preparing alkaline solution
According to CaZn (1-x) OS: stoichiometric ratio of xMn, deionized water, NH 3·H2 O and NH 4HSO4 are proportionally taken in a beaker, the concentration of sulfur element in the obtained alkali solution is 4mol/L, the pH of the obtained alkaline solution is about 9, and the volume of the alkaline solution is 350ml.
Step 3, titrating the acid solution obtained in the step 1 into the alkaline solution at a speed of 10ml/min, and continuously stirring in the titration process at a stirring speed of 500rpm; after the precipitation is finished, heating the reaction system to 90 ℃ in a water bath, preserving heat and purifying for 2 hours, and keeping the magnetic stirring rate unchanged during the period; transferring the conical flask to an ice-water bath, rapidly cooling to 0 ℃ after 30min, washing and filtering with 5L of deionized water, drying, grinding for 20min, and sieving with a 120-mesh sieve to obtain a white precursor.
Step 4, the precursor is subjected to hydrogen gas with the volume ratio of 20% at 750 ℃): calcining for 4 hours under the condition of 80% nitrogen mixed gas to obtain the mechanoluminescence powder.
Step 5, mixing the mechanoluminescence powder with Polydimethylsiloxane (PDMS) according to the following formula 1:2, and curing the mixture at normal temperature to obtain the mechanoluminescence elastomer.
The process parameters of the obtained mechanoluminescence materials are shown in Table 1.
Example 3
The preparation process of the mechanoluminescence material in this example was substantially the same as that of example 2 except that: the incorporation amount of Mn 2+ was 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
Step1, preparing an acidic solution of raw materials
ZnO and Mn (NO 3)2) were weighed according to the stoichiometric ratio of Zn 0.98SMn0.02, respectively, all the raw materials were dissolved in an Erlenmeyer flask with aqua regia to prepare an acidic solution I having a pH of about 1.5, and diluted to 800ml with deionized water to give a total cation concentration of about 0.8mol/L.
Weighing CaO, znO, mnO respectively according to the stoichiometric ratio of CaZn 0.98OSMn0.02, dissolving all raw materials in an conical flask by using aqua regia, and preparing an acidic solution II with the pH of about 1.5; diluted to 800ml with deionized water so that the total cation concentration was about 0.8mol/L.
The acidic solutions I, II were each filtered into a beaker and diluted with deionized water to a total cation concentration of 0.8mol/L in the acidic solution I, II.
Step2, preparing alkaline solution
Deionized water, NH 3·H2 O and NH 4HSO4 are proportionally taken according to the stoichiometric ratio of CaZn 0.98OSMn0.02 n in a beaker, the concentration of sulfur element in the obtained alkali solution is 4mol/L, the pH of the obtained alkaline solution is about 9, and the volume of the alkaline solution is 350ml.
Step 3, firstly, titrating the acid solution I into the alkaline solution according to the speed of 10ml/min, and continuously stirring in the titration process, wherein the stirring speed is 500rpm; then keeping the stirring rotation speed, and titrating the acid solution II into the alkaline solution at the speed of 10 ml/min; after the precipitation is finished, heating the reaction system to 90 ℃ in a water bath, preserving heat and purifying for 2 hours, and keeping the magnetic stirring rate unchanged during the period; transferring the conical flask to an ice-water bath, rapidly cooling to 0 ℃ after 30min, washing and filtering with 5L of deionized water, drying, grinding for 20min, and sieving with a 120-mesh sieve to obtain a white precursor.
Step 4, the precursor is subjected to hydrogen gas with the volume ratio of 20% at 600 ℃): calcining for 4 hours under the condition of 80% nitrogen mixed gas to obtain the mechanoluminescence powder. And is designated as sample F14.
Example 5
Step1, preparing an acidic solution of raw materials
CaCO 3、ZnO、MnCO3 was weighed according to the stoichiometric ratio of CaZn 0.98OSMn0.02, all the raw materials were dissolved in an erlenmeyer flask with aqua regia, and the pH of the prepared acidic solution was about 1.5; diluted to 1000ml with deionized water, the total cation concentration was about 0.8mol/L.
Step2, preparing alkaline solution
Deionized water, NH3.H2O and NH 4HCO3 are proportionally taken in a beaker according to the stoichiometric ratio of CaZn 0.98OSMn0.02, the concentration of bicarbonate radical in the obtained alkali solution is 4mol/L, the pH of the obtained alkali solution is about 9, and the volume of the obtained alkali solution is about 400 milliliters.
Step 3, firstly, titrating an acid solution into an alkaline solution at a speed of 10ml/min, and continuously stirring in the titration process, wherein the stirring speed is 250rpm; the stirring speed was then maintained and after precipitation was completed, the precipitate was filtered, transferred to a conical flask, 300ml of deionized water was added and stirring was continued at 250 rpm. Finally, sodium sulfite is weighed according to the amount of sulfur which is required by stoichiometric ratio and is excessive by 20%, SO 2 gas is introduced into a conical flask containing sediment by controlling the titration speed of 20wt% dilute sulfuric acid to be 1ml/min for reaction to generate sulfur dioxide gas, and the gas is stopped when the pH value of the mixed solution in the conical flask is about 6.0. Heating the reaction system to 90 ℃ in water bath, preserving heat and purifying for 2 hours, and keeping the magnetic stirring rate unchanged during the period; transferring the conical flask to an ice-water bath, rapidly cooling to 0 ℃ after 30min, washing and filtering with 5L of deionized water, drying, grinding for 20min, and sieving with a 120-mesh sieve to obtain a white precursor.
Step 4, the precursor is subjected to hydrogen gas with the volume ratio of 20% at 750 ℃): calcining for 4 hours under the condition of 80% nitrogen mixed gas to obtain the mechanoluminescence powder. And is designated as sample F15.
Example 6
The samples obtained in examples 1-4 were characterized and tested for performance.
The powder samples were subjected to X-ray diffraction spectroscopic analysis and compared with standard samples, typically samples F0, F5, F6, F8, F10, as shown in fig. 1, and it can be seen that the mechanoluminescence material obtained after calcination of the present application was substantially pure phase and only impurities of CaSO 4 having no effect on the luminescence intensity and peak position were generated. Only when the doping concentration of manganese ions is high, because manganese ions occupy the zinc ion sites when weighed in stoichiometric proportions, resulting in a reduced theoretical calculation of zinc ions and ultimately in the formation of calcium sulfate.
The photoluminescence performance analysis of powder samples F0-F10 shows that the excitation peak of the obtained mechanoluminescence powder is 280nm, the emission peak positions are 536nm and 610nm respectively, and the emission peaks of 536nm and 610nm are both caused by 4T1(4G)→6A1 (6S) energy level transition of Mn 2+ as shown in figures 2 and 3.
The luminescence test was performed on sample T4 (CaZn 0.98OSMn0.02), and sample T4 was processed into a cylinder with a diameter of 25mm and a height of 15mm, and the luminescence intensity was measured under different pressure conditions. As shown in fig. 4, the pressure applied to the material was varied in magnitude such that the intensity of the luminescence caused by the force increased with increasing pressure applied to the sample.
The purities of samples F4 and F13 obtained by different dropping sequences at the same calcination temperature were compared, and the results are shown in FIG. 5, and the samples obtained by using CaZn 0.98OSMn0.02 obtained by titrating an acidic solution into an alkaline solution (alkaline salt) are purer than the samples obtained by titrating an alkaline solution into an acidic solution (alkaline salt).
Scanning electron microscope analysis is carried out on the sample F4 (CaZn 0.98OSMn0.02) and the sample F14 (CaZn 0.98OSMn0.02), as shown in fig. 6 and 7, it can be seen that the microscopic morphology of the sample F4 powder is integrated, a core-shell structure is not formed, and the sample F14 powder microscopically forms a layered core-shell structure formed by coating Zn 0.98SMn0.02 and CaZn 0.98OSMn0.02.
CaZn 0.98OSMn0.02 synthesized by adopting a traditional high-temperature solid phase method comprises the following specific steps: raw materials of calcium carbonate, zinc sulfide and manganese carbonate are weighed according to stoichiometric ratio and then are subjected to dry grinding, namely, direct grinding is carried out in a mortar, no reagent such as absolute ethyl alcohol is added, and the grinding time is 1 hour. And (3) placing the ground sample in a nitrogen protective atmosphere, controlling the flow rate of the nitrogen to be 250ml/min, the heating rate to be 10 ℃/min, heating to 1100 ℃, and preserving the heat for 3 hours to obtain a powder sample.
The particle size detection analysis is carried out on the sample F4 and the CaZn 0.98OSMn0.02 sample synthesized by the traditional high-temperature solid phase method, the result is shown in figure 8, the average particle size of the sample F4 obtained by the liquid phase method is about 1.43 mu m (shown in figure 8 a), and the average particle size of the sample obtained by the traditional high-temperature solid phase method is about 5.04 mu m, so that the particle size of the sample obtained by the method is obviously reduced.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (13)
1. 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 type I
AQ (1-x) OS xM II
Wherein A is selected from alkaline earth metal elements;
Q is selected from IIB group elements;
m is selected from any one of transition metal element and lanthanide;
The value range of x is 0.0005-0.15;
the method at least comprises the following steps:
step 1, obtaining an acid solution containing an A source, a Q source and an M source;
obtaining an alkaline solution containing an S source;
Step 2, reacting the acidic solution with the alkaline solution to obtain a precursor;
Step 3, calcining the precursor to obtain the mechanoluminescence material;
in the step 1, an alkaline solution containing an S source is obtained, which comprises:
Dissolving an S source in an alkali solution to obtain an alkali solution containing the S source;
The S source is selected from at least one of NH 4HSO4、（NH4）2SO3·H2O、SO2;
The alkaline solution comprises NH 3·H2 O;
The step 2 specifically includes:
2.1, reacting the acidic solution with the alkaline solution to obtain a reaction solution containing precipitate;
2.2, heating, cooling, filtering and drying the reaction liquid containing the precipitate in sequence to obtain the precursor;
In step 2.2, the heating conditions are as follows:
Heating to 65-90 ℃ and preserving heat for 1-5 h.
2. The method for preparing a mechanoluminescence material according to claim 1, wherein the total concentration of cations in said acidic solution is 0.2 to 0.8 mol/L;
A. the molar concentration ratio of Q, M elements is the stoichiometric ratio of each element in the formula I or the 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 an oxide, a carbonate and a nitrate of M.
3. The method for preparing a mechanoluminescence material according to claim 1, wherein the concentration of S element in said alkaline solution is 0.5 to 3.2mol/L.
4. The method of preparing a mechanoluminescence material according to claim 1, wherein said step 2 comprises:
titrating the acidic solution into the alkaline solution for reaction.
5. The method of claim 1, wherein in step 2.2, the cooling conditions are:
Cooling to 0 ℃ for 10-30 min.
6. The method of claim 1, wherein in step 3, the calcining conditions are:
The calcination temperature is 600-850 ℃, and the calcination time is 2-5 h.
7. The method of preparing a mechanoluminescence material according to claim 1 wherein said calcination is carried out in the presence of a reducing atmosphere.
8. The method of preparing a mechanoluminescence material according to claim 1 wherein in step 1, an acidic solution containing an a source, a Q source, and an M source is obtained comprising:
Adding a source A, a source Q and a source M into an acid solution to obtain the acid solution; or (b)
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 (b)
Adding at least any two of a source A, a source Q and a source M into an acid solution to obtain an acid solution I; then adding at least one of the A source, the Q source and the M source which are different from the composition of the acid solution I into the acid solution to obtain the acid solution II.
9. The method for preparing a luminescent material according to claim 8, wherein the acid solution is selected from any one of aqua regia and concentrated nitric acid solution.
10. The method of preparing a mechanoluminescence material according to claim 8, wherein said step 2 comprises:
Sequentially adding the acid solution of A, the acid solution of Q and the acid solution of M into the alkaline solution according to a certain sequence to react; or (b)
And adding the acid solution I and the acid solution II into the alkaline solution in sequence according to a certain sequence to perform a reaction.
11. The method of preparing a mechanoluminescence material according to any one of claims 1 to 10, characterized in that said method further comprises step 4;
and step 4, mixing the mechanoluminescence material obtained in the step 3 with a high polymer material, and curing to obtain the mechanoluminescence elastomer.
12. The method for preparing a luminescent material according to claim 11, wherein the polymer material is selected from one of polydimethylsiloxane, polyurethane, and polyethylene terephthalate.
13. The method for preparing a mechanoluminescence material according to claim 11, wherein a mass ratio of said mechanoluminescence material to said polymer material is 1:1.5 to 3.5.
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