CN106929018B - A kind of laser protective material and preparation method thereof - Google Patents
A kind of laser protective material and preparation method thereof Download PDFInfo
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- CN106929018B CN106929018B CN201710145426.XA CN201710145426A CN106929018B CN 106929018 B CN106929018 B CN 106929018B CN 201710145426 A CN201710145426 A CN 201710145426A CN 106929018 B CN106929018 B CN 106929018B
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Abstract
The present invention provides a kind of laser protective material, is related to inorganic non-metallic field of functional materials.The chemical formula of the laser protective material is (Sm1‑x‑yYbxEry)2O2S, 0.08≤x≤0.16 and 0.005≤y≤0.02.Utilize Sm3+Transition absorb laser protective material for 1.06 μm and 1.54 μm of near-infrared laser, achieve the purpose that lasing safety.And pass through Yb3+And Er3+Upper transformation, further enhance the lasing safety ability of material.The invention further relates to a kind of preparation methods of laser protective material, comprising: makes Sm, Yb, Er that basic hydrolysis occur and obtains hydrolysate.By hydrolysate, reaction obtains the first product in closing, the first environment heated again.The first product is set to react to obtain the second product in closing, the second environment heated with polyvinylpyrrolidone and thiocarbamide.The preparation method synthesis temperature is low, easy and safe to operate.
Description
Technical field
The present invention relates to inorganic non-metallic field of functional materials, and in particular to a kind of laser protective material and its preparation side
Method.
Background technique
Laser has been widely used in work due to having the characteristics that brightness height, good directionality, being not easy to be disturbed, bandwidth
Industry, business, scientific research, medical treatment and military affairs etc..But since laser energy density is high and energy is concentrated, it is possible to people
The shone position of body generates very major injury.As laser energy is continuously improved, laser kind is continuously increased and laser application
Range constantly expands, and the destruction that laser regards force-summing device to personnel is also increasingly severe, and especially 1.06 μm, 1.54 μm etc.
Near-infrared laser, therefore carried out to the Protective Research of laser damage is also synchronous.However, in existing laser protective material, it is general
It is actually rare all over the research using high molecular material and glass material, and for the powder body material of lasing safety, it is anti-for laser
The powder functional material for protecting coating material selection is less.
Summary of the invention
The purpose of the present invention is to provide a kind of laser protective material, this laser protective material is directed to 1.06 μm, 1.54 μm
Equal near-infrared lasers have good protection effect.
Another object of the present invention is to provide a kind of preparation method of laser protective material, the preparation method synthesis temperatures
Low, easy and safe to operate, laser protective material obtained has good protective capacities.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention proposes that a kind of laser protective material, the chemical formula of the laser protective material are (Sm1-x-yYbxEry)2O2S,
Wherein, 0.08≤x≤0.16 and 0.005≤y≤0.02.
The present invention proposes a kind of preparation method of laser protective material comprising: make Sm, Yb, Er that basic hydrolysis occur and obtains
To hydrolysate.By hydrolysate, reaction obtains the first product in closing, the first environment heated again.Make the first product and gathers
The reaction in closing, the second environment heated of vinylpyrrolidone and thiocarbamide obtains the second product.
The beneficial effect of the laser protective material of the embodiment of the present invention and preparation method thereof is: utilizing rare-earth Sm3+'s6H5/2
Ground state to6F9/2Excitation state,6H13/2The transition of excitation state makes (Sm1-x-yYbxEry)2O2S is at 1.05~1.15 μm and 1.50~1.65
In μm two wavelength bands, it can be absorbed for 1.06 μm and 1.54 μm of near-infrared laser, achieve the purpose that lasing safety.
Sm2O2S special hex crystal structure has more spacious space structure, allows a certain amount of cation and anion vacancy shape
At and a certain amount of gap ion enter, and crystal structure is held essentially constant, so that Yb3+And Er3+It is able to enter Sm2O2S's
(Sm is formed in lattice1-x-yYbxEry)2O2S。Yb3+And Er3+It can by being converted to the near-infrared laser of 1.06 μm and 1.54 μm
It is light-exposed, further enhance (Sm1-x-yYbxEry)2O2The lasing safety ability of S.The laser protective material can be used as coating material
It uses, is applied to various fields.In the preparation method of laser protective material, using thiocarbamide as sulphur source, experimental implementation ensure that
The personal safety of personnel.And (Sm further is controlled using polyvinylpyrrolidone1-x-yYbxEry)2O2The pattern of S is sheet, is mentioned
The lasing safety ability of high material.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the XRD diffracting spectrum of the laser protective material of the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscopic picture of the laser protective material of the embodiment of the present invention 1；
Fig. 3 is that diffusing reflection of the laser protective material of the embodiment of the present invention 1 in 0.90~1.15 μ m wavelength range absorbs
Spectrogram；
Fig. 4 is that diffusing reflection of the laser protective material of the embodiment of the present invention 1 in 1.30~1.65 μ m wavelength ranges absorbs
Spectrogram；
Fig. 5 is up-conversion fluorescence spectrogram of the laser protective material of the embodiment of the present invention 1 under 1.06 μm of laser excitation；
Fig. 6 is up-conversion fluorescence spectrogram of the laser protective material of the embodiment of the present invention 1 under 1.54 μm of laser excitation.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Laser protective material of the embodiment of the present invention and preparation method thereof is specifically described below.
A kind of laser protective material, the chemical formula of laser protective material are (Sm1-x-yYbxEry)2O2S, wherein 0.08≤x
≤ 0.16 and 0.005≤y≤0.02.Further, 0.1≤x≤0.12 and 0.01≤y≤0.02.
The laser protective material utilizes rare-earth Sm3+'s6H5/2Ground state to6F9/2Excitation state,6H13/2The transition of excitation state makes
(Sm1-x-yYbxEry)2O2S can be directed to 1.06 μm and 1.54 in 1.05~1.15 μm and 1.50~1.65 μm of two wavelength bands
μm near-infrared laser absorbed, achieve the purpose that lasing safety.In conjunction with Yb3+、Er3+To 1.06 μm, 1.54 μm of laser
Upper transformation (near-infrared laser of 1.06 μm and 1.54 μm is converted into visible light), further increase the laser of material
Protective capacities.Wherein, mainly Er3+Upper transformation is risen to the laser of 1.06 μm, 1.54 μm, Er is used alone3+When, it is made
Material (Sm1-yEry)2O2S is weaker to the conversion effect of laser.Therefore Yb is used3+Enhance Er3+To the transfer capability of laser, system
(the Sm obtained1-x-yYbxEry)2O2S is to the upper transfer capability of laser compared with (Sm1-yEry)2O2S is strong.
Individually doping Er3+When, Er3+Excessive concentration will appear concentration quenching under high doping.And Er3+/Yb3+The energy being co-doped in system
Level structure includes Er3+And Yb3+Two level systems, Yb3+For simple dual intensity level structure, Excited-state Absorption and energy is not present
Transfer problem in amount.In Er3+/Yb3+It is co-doped in system, Yb3+Concentration is greater than Er3+Concentration a, so that Er3+By multiple Yb3+Packet
It encloses, avoids Er3+Cluster it is poly-, blocked in Er3+When concentration improves, Er3+Mutually too close to and the case where form ion pair.
Because of an Er3+Surrounding is by several Yb3+Ion is surrounded, so Er3+The probability very little that laser is activated directly is absorbed, it is main
That absorb laser energy is Yb3+, and Yb3+Ion is absorbed as main energetic, absorption line is very wide.In this doping body
It is by Yb in system3+Energy is first absorbed, Er is then excited by sensibilization3+, make Er3+Energy level transition occurs, to make full use of
Ytterbium ion absorption band is very wide, pump absorption coefficient is big, the advantages of allowing high power multimode to pump.
The pattern of laser protective material has a certain impact to its performance tool, by reasonable design, makes it have bigger
Specific surface area, can play a role in improving to laser absorption performance.Preferably, in the embodiment of the present invention, the laser of preparation is anti-
Protective material has laminated structure.The laser protective material of laminated structure has biggish absorption area, therefore can increase material
To the protective capacities of laser.
Preferably, with laminated structure laser protective material with a thickness of 3~5 μm, it is highly preferred that with a thickness of 3~4.5
μm, it is further preferred that thickness can be 3.5~4 μm.The thickness of laser protective material laminated structure should be suitable for, too it is thick then
It is unfavorable for Sm3+、Er3+、Yb3+Play its safeguard function.Certainly it can also adopt with other methods, by the sheet thickness control of material
System is in smaller range.
A kind of preparation method of laser protective material, comprising: make Sm, Yb, Er that basic hydrolysis occur and obtain hydrolysate.Again
By hydrolysate, reaction obtains the first product in closing, the first environment heated.Make the first product and polyvinylpyrrolidone
Reaction obtains the second product in closing, the second environment heated with thiocarbamide.
In preparation process, toxic sulfurous gas is not used, but uses thiocarbamide as sulphur source, ensure that experimental implementation people
The personal safety of member.Thiocarbamide also further provides reproducibility environment, convenient for synthesis oxysulfide.Utilize polyvinylpyrrolidone
(Sm is controlled as structural approach agent1-x-yYbxEry)2O2The pattern of S is sheet, improves the lasing safety ability of material.
Preferably, Sm, Yb, Er are with one of nitrate and its hydrate, chlorate and its hydrate or a variety of
Form is provided.For example, the form provided can be Sm (NO3)3·6H2O、SmCl3·6H2O、Yb(NO3)3·5H2O、
YbCl3·6H2O、Er(NO3)3·5H2O、ErCl3·6H2O。
For example, when Sm, Yb, Er are with Sm (NO3)3·6H2O、Yb(NO3)3·5H2O and Er (NO3)3·5H2The form quilt of O
When offer, making Sm, Yb, Er that the method for basic hydrolysis occur includes: by Sm (NO3)3·6H2O、Yb(NO3)3·5H2O and Er
(NO3)3·5H2O is dissolved in water to obtain mixing salt solution, and the pH of mixing salt solution is adjusted to 9~10.PH is 9~10
In alkaline aqueous solution, basic hydrolysis is the most thorough, is conducive to the yield for improving the first product of later period.Certainly, Sm, Yb, Er can also
To be provided in the form of the oxide, recycles nitric acid or hydrochloric acid to carry out the processing in later period to oxide, obtain water-soluble samarium
Salt, ytterbium salt, erbium salt.
Preferably, the method that hydrolysate reacts in closing, the first environment heated includes that indwelling is had hydrolysate
Water heating kettle be heated to 160~200 DEG C, and under the conditions of 160~200 DEG C keep the temperature 18~32h.It is obtained after 18~32h of heat preservation
First product is hydroxide, and hydroxide includes being doped in samaric hydroxide, ytterbium hydroxide, erbium hydroxide and lattice
Yb3+And Er3+Samaric hydroxide.
Preferably, the side that the first product reacts in closing, the second environment heated with polyvinylpyrrolidone and thiocarbamide
Method includes, and the water heating kettle that indwelling has the first product, polyvinylpyrrolidone and thiocarbamide is heated to 180~220 DEG C, and
20~32h is kept the temperature under conditions of 180~220 DEG C.The second product obtained after 20~32h of heat preservation includes being doped in lattice
Yb3+And Er3+Sm2O2S, finally with chemical formula (Sm1-x-yYbxEry)2O2S is indicated.
Water heating kettle, respectively as reaction vessel, has excellent in first environment and second environment using water heating kettle itself
Leakproofness can meet the requirement of temperature and pressure simultaneously under easy operation, improve reaction rate and product yield.
Certainly, in other embodiments of the invention, enclosed environment can also be provided using the reaction vessel other than water heating kettle, as long as should
Reaction vessel can guarantee that chemical reaction is normally carried out under high temperature and pressure.Because water heating kettle is common experimental facilities, valence
Lattice are cheap, easy to operate, therefore are all made of water heating kettle in the embodiment of the present invention and provide closed reaction environment.
Preferably, every (Sm for preparing 1mmol1-x-yYbxEry)2O2S makes the first product and polyvinylpyrrolidone and sulphur
Urea closing, heating second environment in reaction obtain the second product the step of in, need 4~4.4g of polyvinylpyrrolidone,
0.3~0.5g of thiocarbamide.Inventor pass through experimental studies have found that, polyvinylpyrrolidone is added with aforementioned proportion and when thiocarbamide, material
The laminated structure control of material preferably, and also avoids wasting caused by material rate is improper.More preferably, polyethylene can be used
4.1~4.3g of pyrrolidones, 0.2~0.4g of thiocarbamide carry out better pattern control and provide reaction dosage more appropriate sulphur
Source.
Preferably, the second product is dried in 50~70 DEG C.It is used for the ease of storage and later period, by the second product in 50
~70 DEG C of drying.Second product has just obtained the higher laser protective material (Sm of purity after washing and drying1-x-yYbxEry)2O2S.Drying temperature is excessively high, easily causes reunion, and the product after reunion is directly using will affect its lasing safety ability.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
Prepare 1mmol (Sm0.915Yb0.08Er0.005)2O2S weighs required raw material 0.8134g Sm (NO3)3·6H2O、
0.0719g Yb(NO3)3·5H2O and 0.0044g Er (NO3)3·5H2O, completely dissolve in water be made nitrate mixing it is molten
Liquid stirs evenly；The pH value of rare earth nitrate solution is adjusted, until the pH stable of rare earth nitrate solution is to 10；It will mix up
The rare earth nitrate solution of pH value is placed in autoclave, after reacting 32h under the conditions of 160 DEG C, is naturally cooling to room temperature, will
Product is washed with water 3 times, and dehydrated alcohol is added, stirs evenly；4.4g polyvinylpyrrolidone and 0.3045g thiocarbamide are weighed, it is complete
Fully dissolved stirs evenly in mixed liquor；The mixed liquor stirred evenly is placed in autoclave, it is anti-under the conditions of 220 DEG C
After answering 32h, it is naturally cooling to room temperature, the product after reaction is washed 4 times with dehydrated alcohol；Product after washing is dried at 50 DEG C
It is dry, obtain laser protective material.
Embodiment 2
Prepare 1mmol (Sm0.895Yb0.10Er0.005)2O2S weighs required raw material 0.7957g Sm (NO3)3·6H2O、
0.0898g Yb(NO3)3·5H2O and 0.0044gEr (NO3)3·5H2O is completely dissolved in water and nitrate mixed solution is made,
It stirs evenly；The pH value of rare earth nitrate solution is adjusted, until the pH stable of rare earth nitrate solution is to 9.8；PH will be mixed up
The rare earth nitrate solution of value is placed in autoclave, after reacting 29h under the conditions of 170 DEG C, is naturally cooling to room temperature, will be produced
Object is washed with water 4 times, and dehydrated alcohol is added, stirs evenly；4.3g polyvinylpyrrolidone and 0.3425g thiocarbamide are weighed, completely
It is dissolved in mixed liquor, stirs evenly；The mixed liquor stirred evenly is placed in autoclave, is reacted under the conditions of 210 DEG C
After 30h, it is naturally cooling to room temperature, the product after reaction is washed 5 times with dehydrated alcohol；Product after washing is dried at 55 DEG C
It is dry, obtain laser protective material.
Embodiment 3
Prepare 1mmol (Sm0.87Yb0.12Er0.01)2O2S weighs required raw material 0.7734g Sm (NO3)3·6H2O、
0.1078g Yb(NO3)3·5H2O and 0.0089g Er (NO3)3·5H2O, completely dissolve in water be made nitrate mixing it is molten
Liquid stirs evenly；The pH value of rare earth nitrate solution is adjusted, until the pH stable of rare earth nitrate solution is to 9.6；It will mix up
The rare earth nitrate solution of pH value is placed in autoclave, after reacting 26h under the conditions of 180 DEG C, is naturally cooling to room temperature, will
Product is washed with water 5 times, and dehydrated alcohol is added, stirs evenly；4.2g polyvinylpyrrolidone and 0.3806g thiocarbamide are weighed, it is complete
Fully dissolved stirs evenly in mixed liquor；The mixed liquor stirred evenly is placed in autoclave, it is anti-under the conditions of 200 DEG C
After answering 28h, it is naturally cooling to room temperature, the product after reaction is washed 6 times with dehydrated alcohol；Product after washing is dried at 60 DEG C
It is dry, obtain laser protective material.
Embodiment 4
Prepare 1mmol (Sm0.845Yb0.14Er0.015)2O2S weighs required raw material 0.7512g Sm (NO3)3·6H2O、
0.1258g Yb(NO3)3·5H2O and 0.0133g Er (NO3)3·5H2O, completely dissolve in water be made nitrate mixing it is molten
Liquid stirs evenly；The pH value of rare earth nitrate solution is adjusted, until the pH stable of rare earth nitrate solution is to 9.4；It will mix up
The rare earth nitrate solution of pH value is placed in autoclave, after reacting 23h under the conditions of 180 DEG C, is naturally cooling to room temperature, will
Product is washed with water 3 times, and dehydrated alcohol is added, stirs evenly；4.2g polyvinylpyrrolidone and 0.3806g thiocarbamide are weighed, it is complete
Fully dissolved stirs evenly in mixed liquor；The mixed liquor stirred evenly is placed in autoclave, it is anti-under the conditions of 200 DEG C
After answering 26h, it is naturally cooling to room temperature, the product after reaction is washed 4 times with dehydrated alcohol；Product after washing is dried at 60 DEG C
It is dry, obtain laser protective material.
Embodiment 5
Prepare 1mmol (Sm0.82Yb0.16Er0.02)2O2S weighs required raw material 0.7290g Sm (NO3)3·6H2O、
0.1437g Yb(NO3)3·5H2O and 0.0177g Er (NO3)3·5H2O, completely dissolve in water be made nitrate mixing it is molten
Liquid stirs evenly；The pH value of rare earth nitrate solution is adjusted, until the pH stable of rare earth nitrate solution is to 9.2；It will mix up
The rare earth nitrate solution of pH value is placed in autoclave, after reacting 20h under the conditions of 190 DEG C, is naturally cooling to room temperature, will
Product is washed with water 4 times, and dehydrated alcohol is added, stirs evenly；4.1g polyvinylpyrrolidone and 0.4187g thiocarbamide are weighed, it is complete
Fully dissolved stirs evenly in mixed liquor；The mixed liquor stirred evenly is placed in autoclave, it is anti-under the conditions of 190 DEG C
After answering for 24 hours, it is naturally cooling to room temperature, the product after reaction is washed 5 times with dehydrated alcohol；Product after washing is dried at 65 DEG C
It is dry, obtain laser protective material.
Embodiment 6
Prepare 1mmol (Sm0.90Yb0.08Er0.02)2O2S weighs required raw material 0.8001g Sm (NO3)3·6H2O、
0.0719g Yb(NO3)3·5H2O and 0.0177g Er (NO3)3·5H2O, completely dissolve in water be made nitrate mixing it is molten
Liquid stirs evenly；The pH value of rare earth nitrate solution is adjusted, until the pH stable of rare earth nitrate solution is to 9；PH will be mixed up
The rare earth nitrate solution of value is placed in autoclave, after reacting 18h under the conditions of 200 DEG C, is naturally cooling to room temperature, will be produced
Object is washed with water 5 times, and dehydrated alcohol is added, stirs evenly；4.0g polyvinylpyrrolidone and 0.5000g thiocarbamide are weighed, completely
It is dissolved in mixed liquor, stirs evenly；The mixed liquor stirred evenly is placed in autoclave, is reacted under the conditions of 180 DEG C
After 20h, it is naturally cooling to room temperature, the product after reaction is washed 6 times with dehydrated alcohol；Product after washing is dried at 70 DEG C
It is dry, obtain laser protective material.
Embodiment 7
Prepare 1mmol (Sm0.90Yb0.08Er0.02)2O2S weighs required raw material 0.6567g SmCl3·6H2O、0.0620g
YbCl3·6H2O and 0.0153g ErCl3·6H2O is completely dissolved in water and chloride mixed solution is made, stirs evenly；It adjusts
The pH value of rare-earth chloride solution is saved, until the pH stable of rare-earth chloride solution is to 9；The rare earth-iron-boron of pH value will be mixed up
Solution is placed in autoclave, after reacting 18h under the conditions of 200 DEG C, is naturally cooling to room temperature, product is washed with dehydrated alcohol
It washs 5 times, dehydrated alcohol is added, stirs evenly；4.0g polyvinylpyrrolidone and 0.5002g thiocarbamide are weighed, is dissolved completely in mixed
It closes in liquid, stirs evenly；The mixed liquor stirred evenly is placed in autoclave, after reacting 20h under the conditions of 180 DEG C, from
It so is cooled to room temperature, the product after reaction is washed 6 times with dehydrated alcohol；Product after washing is dried at 68 DEG C, is swashed
Photoprotection material.
Test example 1
The XRD material phase analysis and microstructure of laser protective material are tested.
Object phase is carried out to laser protective material provided by Examples 1 to 7 with X-ray diffractometer (XRD, D/Max2500)
Composition analysis, and Morphology analysis is carried out using scanning electron microscope (SEM, JEOL-6310).
The test result of Examples 1 to 7 is essentially identical, this is analyzed for sentencing the test result of embodiment 1.Fig. 1
For the XRD diffracting spectrum of laser protective material provided by embodiment 1.It will be seen from figure 1 that the position of main diffraction peak all with
Six side Sm2O2S is corresponding, and exists without the peak of other substance phases.Illustrate Yb3+And Er3+It has been into Sm2O2The lattice of S
In, and do not destroy Sm2O2The crystal structure of S, does not influence Sm3+Laser absorption ability.Fig. 2 is to swash provided by embodiment 1
The SEM test result of photoprotection material, the test result of scanning electron microscope show that micron-sized laminated structure is presented in sample particle, put down
With a thickness of 3~5 μm.
Test example 2
The diffusing reflection absorption spectrum of laser protective material is tested.
Using UV3600 type ultraviolet-visible light-near infrared spectrometer at room temperature to provided by Examples 1 to 7
Laser protective material carries out the test of two waveband diffusing reflection absorption spectrum, 0.90~1.15 μm of wavelength band of test and 1.30~1.65
μm.By taking embodiment 1 as an example, the test result of embodiment 1 is shown in Fig. 3 and Fig. 4.From figure 3, it can be seen that due to Sm3+Energy level transition is deposited
In two peak absorbing bands of 900~1000nm and 1000~1150nm, two absorption bands correspond respectively to Sm3+Two energy levels
Transition6H5/2→6F11/2With6H5/2→6F9/2, light reflectivity is below 1%.As can be seen from Figure 4 in 1.30~1.65 mum wavelengths
In range, due to Sm3+Energy level transition, there is a broad peak absorption bands, correspond to Sm3+Energy level transition6H5/2→6H13/2, light
Reflectivity is below 1%.
Table 1 is diffusing reflection rate value of the laser protective material at 1.06 μm and 1.54 μm provided by Examples 1 to 7.
1 diffusing reflection absorption spectrum test result of table
Table 1 is diffusing reflection rate value of the Examples 1 to 7 at 1.06 μm and 1.54 μm, as it can be seen from table 1 the present invention is real
It applies laser protective material provided by example 1~7 and can reach 0.682%-0.719% in wavelength for the diffusing reflection rate at 1.06 μm.
Meanwhile it can reach 0.496%-0.549% in 1.54 μm of diffusing reflection rate.
Test example 3
Up-conversion fluorescence spectrum test of the laser protective material under 1.06 μm of excitations.
Multiple spectra response type luminescent material provided by Examples 1 to 7 is carried out using F4600 type Fluorescence Spectrometer
Fluorescence spectrum test under 1.06 μm of near infrared light excitations, tests 550~900nm of wavelength band, with the test result of embodiment 1
For analyzed, test result is shown in Fig. 5.
From fig. 5, it can be seen that multiple spectra response type luminescent material provided by the embodiment of the present invention 1 is close at 1.06 μm of wavelength
The infrared ray excited lower feux rouges for issuing 664nm, derives from Er3+'s4F9/2→4I15/2Energy level transition, have up-conversion luminescence effect
It answers.
Test example 4
Up-conversion fluorescence spectrum test of the laser protective material under 1.54 μm of excitations.
Multiple spectra response type luminescent material provided by Examples 1 to 7 is carried out using F4600 type Fluorescence Spectrometer
Fluorescence spectrum test under 1.54 μm of near infrared light excitations, tests 500~750nm of wavelength band, with the test result of embodiment 1
For analyzed, test result is shown in Fig. 6.
From fig. 6, it can be seen that multiple spectra response type luminescent material provided by the embodiment of the present invention 1 is close at 1.54 μm of wavelength
Infrared ray excited lower sending feux rouges and green light.Feux rouges derives from Er3+'s4F9/2→4I15/2Energy level transition, green light derive from Er3+
's2H11/2、4S3/2→4I15/2Energy level transition.
In conclusion laser protective material provided by the invention have to 1.06 μm and 1.54 μm of near-infrared lasers absorb and
The upper difunctional effect of conversion, has effectively achieved the purpose that lasing safety.The preparation method of laser protective material provided by the invention,
Micron-sized laminated structure is presented in sample particle, and average thickness is 3~5 μm, and preparation process does not use toxic sulfurous gas, tool
Have the advantages that synthesis temperature is low, easy and safe to operate.Laser protective material provided by the invention can be applied to lasing safety with it is hidden
Body functional material etc..
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of laser protective material, which is characterized in that the chemical formula of the laser protective material is (Sm1-x-yYbxEry)2O2S,
Wherein, 0.08≤x≤0.16 and 0.005≤y≤0.02.
2. laser protective material according to claim 1, which is characterized in that 0.1≤x≤0.12 and 0.01≤y≤0.02.
3. laser protective material according to claim 1 or 2, which is characterized in that the laser protective material has sheet
Structure.
4. laser protective material according to claim 3, which is characterized in that the laser with the laminated structure is anti-
Protective material with a thickness of 3~5 μm.
5. a kind of preparation method of laser protective material as described in claim 1, which is characterized in that make Sm, Yb, Er that alkali occur
Property hydrolyze to obtain hydrolysate, then by the hydrolysate closing, heating first environment in reaction obtain the first product, make
First product reacts to obtain the second product with polyvinylpyrrolidone and thiocarbamide in closing, the second environment heated.
6. the preparation method of laser protective material according to claim 5, which is characterized in that the Sm, the Yb, described
Er is provided with one of nitrate and its hydrate, chlorate and its hydrate or a variety of forms；As the Sm, institute
State Yb, the Er is with Sm (NO3)3·6H2O、Yb(NO3)3·5H2O and Er (NO3)3·5H2When the form of O is provided, make institute
Stating Sm, the Yb, the Er method of basic hydrolysis occurs includes: by the Sm (NO3)3·6H2O, the Yb (NO3)3·
5H2The O and Er (NO3)3·5H2O is dissolved in water to obtain mixing salt solution, and the pH of the mixing salt solution is adjusted to 9
~10.
7. the preparation method of laser protective material according to claim 5, which is characterized in that the hydrolysate is sealing
The method reacted in the first environment close, heated includes, the water heating kettle that indwelling has the hydrolysate is heated to 160~
200 DEG C, and 18~32h is kept the temperature under the conditions of 160~200 DEG C.
8. according to the preparation method of the described in any item laser protective materials of claim 5~7, which is characterized in that described first
Product and the polyvinylpyrrolidone and the thiocarbamide closing, heating the second environment in the method reacted include,
There is the water heating kettle of first product, the polyvinylpyrrolidone and the thiocarbamide to be heated to 180~220 DEG C indwelling,
And 20~32h is kept the temperature under conditions of 180~220 DEG C.
9. laser protective material preparation method according to claim 5, which is characterized in that by second product in 50~
70 DEG C of drying.
10. the preparation method of laser protective material according to claim 5, which is characterized in that every to prepare the described of 1mmol
(Sm1-x-yYbxEry)2O2S, make first product and the polyvinylpyrrolidone and the thiocarbamide in closing, heating
In the second environment in reaction the step of obtaining second product, the 4~4.4g of polyvinylpyrrolidone, described is needed
0.3~0.5g of thiocarbamide.
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