A new red luminescent powder and a method for making red luminescent ceramics

A new red luminescent powder is composed of BEiyQia8_x_yZnxTi03:aPr3+, bLu3+, cNa+ and dB3+, with titanate as the substrate, Pr3+ as the activator and Lu3+ as the sensitizer. The luminous powder is used to prepare the luminous red ceramics.
The best known green luminescent powder is SrAl2O4 = Eu2+ and Dy3+, while the blue luminescent powder is SrAl2O4 = Eu2+ and Nd3+. The chemical properties, afterglow intensity and attenuation time of these two luminescent powder are similar. But there is no red luminous powder that matches its performance. In terms of chromaticity, as long as there are three primary colors (red, green and blue) with stable chemical properties and similar afterglow intensity and decay time, they can be mixed in a certain proportion to get a luminous powder of any color. Otherwise, the afterglow color of the mixed materials will change in the decay process. The red noctilucent powder has been found to have four kinds of alkaline earth metal sulfide system according to the matrix; Sulfur oxide system; Strontium aluminum complex sulfur oxide system; Alkaline earth metal titanate system. Although the luminescent materials of the first three systems all have good red long afterglow properties, their application is limited by the fact that sulfur-containing materials are prone to decay and give off a foul odor in humid air. Pr3+ activated alkaline earth metal titanate MTiO3 (M = Ca, Sr, Ba) red luminous powder is a kind of red long afterglow luminescent material with stable performance, but the luminance and afterglow time do not meet the practical requirements.

The technical problem to be solved by the invention is to provide a synthesis method of all-weather stable alkaline earth metal titanate red noctilucent powder and its application method on noctilucent ceramics. In addition to the slow red long afterglow property, this kind of luminescent material also has strong light absorption property in the ultraviolet region of 380nm and 450-550nm, and is a kind of energy-saving material that can promote the storage of solar energy. The technical solution to the technical problem of the invention is the red long afterluminescence materials used by the composition of the general formula is BayC^^qaiJiO^aPr3+, bLu3+, cNa+, dB3+,0≤ ≤ 0.3, O≤y≤ 0.01,0≤ A ≤ 0.05,0≤ B ≤ 0.05,0≤ C ≤ 0.01, O≤d≤ 0.1, and Y are not the same as O. The maximum excitation wavelength is 380nm and 440590nm, and the maximum emission wavelength is 613nm. This red noctilucent powder is a kind of preparation that can be used on noctilucent ceramics. BayCaO. 8_x-yZnxTi03 aPr3+, bLu3+, cNa+, dB3+ have two significant properties: one is the slow red afterglow, the other is that it can be used to prepare high-temperature red noctilucent ceramics. The invention has the following characteristics: 1. A synthetic method for preparing CaTi03/Ca2Zn4Ti 16038 by the Pr measurement ratio of CaO. 8ZnO. 2Ti03:Pr. A new method for calculating the ratio of raw materials – inverse calculation method was designed. Phosphor powders consisting of CaTi03 and Ca2Zn4Ti 16038 were successfully synthesized by the improved method. 2. Combining the above new phosphor (BCZT:PLNB) with glaze, the luminous red ceramics for architecture is synthesized. The luminous red ceramics can store the solar energy during the day and slowly glow at night, which is a kind of energy-saving and environment-friendly building material.
3. Applying the new phosphor powder (BCZT:PLNB) to the painting of “Chinese red” porcelain can produce the artistic ceramics visible in red day and night. 4. The luminescent materials referred to in the present invention can also be used in the fields of building materials, industrial arts and other fields to synthesize red luminous coatings and other indicative materials. The red luminescent powder synthesis method mentioned in the present invention refers to: 1. Ingredients Sol-gel method According to the reaction equation (0.8-x-y)CaC03+xZn0+yBaC03+Ti02 = BayCaO. 8-x-yznxti03apr3 +, bLu3+, cNa+, dB3++C02 add citric acid into the hexadiol liquid according to the stoichiometric ratio, stir it to dissolve it by magnetic force, and then add Ti (0C4H9) 4 to stir the solution (I) by magnetic force. (2) According to the measurement ratio, take Ca(N03)2, Zn(N03)2, NaN03, Pr(N03)3 solutions with pipette, mix them, heat water bath to evaporate the water, and concentrate them to one third of the initial volume to get solution (II). Add solution II to solution I drop by drop under magnetic stirring to obtain the mixture (III); The mixture (III) was maintained at a constant temperature of 200°C for 2 5h to obtain a brown and black thick material; (5) Maintain a constant temperature of 1 pool at 400°C, cool it, grind it into powder, and set it for use. (1) High-temperature solid-phase synthesis The crucible with ingredients was placed in a high-temperature furnace. The ingredients obtained by the dry and wet methods were burned for 48 96h at 1200 1300°C, and the powder obtained by the sol-gel method was burned for 2h at 1000°C, and the red long afterglow luminescent materials Bayqic.8_x_yaixti03 :aPr3+, bLu3+, cNa+, dB3+ were obtained. (2) Microwave radiation synthesis The crucible with ingredients was placed in the microwave oven, microwave power was selected, and the temperature was controlled at 700 900°C to maintain heating for 90min and then cooled to obtain red long afterglow luminescent materials BayQia8_x_yaixTi03:aPr3+, bLu3+, cNa+, dB3+.
The specific embodiments of the invention are as follows: citric acid (A.r.), ethylene glycol (A.r.), H3BO3 (A.r.), Ti (OC4H9) 4 (A.R.), Ca(NO3)2 · 4H20(A.r.), Zn (NO3)2 · 6H20(A.r.), Pr6O11 (99.99%), and NaCl (A. R.), which are used as reagents, are accurately called I^r6O1Jn NaCl. I^r6O11 was dissolved with concentrated hydrochloric acid, the excess hydrochloric acid was heated to evaporate, then NaCl was added, then deionized water was added to dissolve and volume was determined, and the mixture was prepared with ft·3+ and Na+ concentrations of 2 X IOo-5Hiol · ml-1. Ca(NO3)2 · 4H20 and Ba(NO3)2 · 4H20 crozn (NO3)2 · 6H20 were accurately weighed and prepared into solutions with a concentration of 0.2 mol · L-1, respectively. According to the principle of electrical neutrality of the material and the research results in the literature, the nitrate solution of Ba2+, Ca2+, Zn2+, ft·3+ and Na+ was mixed with each other uniformly according to the calculated ratio of chemical formula BaycaA8_yzna2ti03:ft ·3+, Lu3+ and Na+. The required Ti(OC4H9)4 was accurately weighed according to the metering ratio, and was slowly dropped into the pre-prepared mixed solution of citric acid and glycol [Ti(OC4H9)4, citrate glycol =3g Ig 6.7g], and fully stirred. Then add the nitrate mixture drop by drop into the ethylene glycol solution of tebutyl titanate and continue to stir LH with a magnetic agitator to obtain a yellowish solution. The solution was placed in a 90°C water bath to evaporate excess water and form a yellowish transparent sol. Transfer the solution to the evaporating dish while it is hot, and continue drying for 12h in a constant temperature drying oven at 200°C to obtain the brown dry gel. The dry gel is put into a high temperature furnace and treated in a 400°C tank, and then ground into a black powder (precursor). Finally, the precursor was placed in a program-controlled temperature furnace, calcined at 950°C for 21h, cooled and ground evenly to obtain the sample. Add 0.6m0L % H3BO3 as flux. Ig luminous powder was mixed with IOg gelatin to make paste, and then painted or wrote on the red porcelain. The red luminous ceramic was fired at 1200°C for 1 hour. Ig luminescent powder is mixed with 5g glaze, mixed into paste, coated on ceramic substrate, and fired at 1200°C for 1 hour to obtain red luminescent ceramics.
1. A new red nightlight powder is based on the titanium salt, Pr3+ as activator, Lu3+ as sensitiator, its composition is baycii0.8_x_yznxti03 :aPr3+, bLu3+, cNa+, dB3+,0 case 0. 3,0 y case 0. 01,0 a case 0. 005,0 b case 0.
The red noctilucent powder is characterized in that its maximum excitation wavelength is 350nm and 470580nm, and its maximum emission wavelength is 613nm.
The preparation method of the red noctilucent powder — a new method for calculating the ratio of raw materials — inverse calculation method. Phosphors with phase composition only CaTiO3 and Ca2Zn4Ti16O38 were successfully synthesized by the improved method.

The invention relates to a red noctilucent powder and its red noctilucent ceramics. The new red luminescent powder is composed of Bayca0.8-x-yznxTiO3 :aPr3+, bLu3+, cNa+, dB3+, 0≤ X ≤0.3, 0≤y≤0.01, 0≤a≤0.005, 0≤ B ≤0.005, 0≤ C ≤0.01, 0≤ D ≤0.1, x and Y are equal to 0 when they are different. The red noctilucent powder is characterized by its maximum excitation wavelength of 350nm and 470nm ~ 580nm, and maximum emission wavelength of 613nm. A new method of calculating the ratio of raw materials – backward calculation and measurement method was used to prepare red luminous powder. Phosphors with phase composition only CaTiO3 and Ca2Zn4Ti16O38 were successfully synthesized by the improved method. The application method of red luminous powder is characterized in that it can be fused with glaze to make red luminous architectural ceramics. Can be painted on ceramic products to prepare red luminous art ceramics.