CN108441175A - Lead tungstate shell phase-change microcapsule and preparation method thereof - Google Patents
Lead tungstate shell phase-change microcapsule and preparation method thereof Download PDFInfo
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- CN108441175A CN108441175A CN201810389487.5A CN201810389487A CN108441175A CN 108441175 A CN108441175 A CN 108441175A CN 201810389487 A CN201810389487 A CN 201810389487A CN 108441175 A CN108441175 A CN 108441175A
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- 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
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- G—PHYSICS
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- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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Abstract
The invention discloses a kind of lead tungstate shell phase-change microcapsules and preparation method thereof, including：Phase-change material, citrate, emulsifier solution and deionized water are mixed, emulsification obtains phase change material emulsion；Lead salt solution is taken to instill in phase change material emulsion, then tungstate solution is instilled phase change material emulsion by stirring, stir, and lead salt and tungstates generate lead tungstate by precipitation reaction and be deposited on phase-change material emulsion droplet surface, form the shell of cladding core material；System after reaction is cooled to room temperature, phase-change microcapsule is taken out, is washed with deionized, dries, obtains lead tungstate shell phase-change microcapsule.Lead tungstate shell phase-change microcapsule prepared by the present invention solves the problems, such as the leakage of phase-change material, phase separation and supercooling and the not high technical problem of thermal conductivity.Meanwhile the shielding gamma-rays that has of lead tungstate shell and paraffin phase change material and neutron ability, also make the lead tungstate shell phase-change microcapsule have phase-change accumulation energy and radiation protection difunctional.
Description
Technical field
The invention belongs to technical field of function materials, are related to phase-changing energy storage material and radiation proof material, can extensive use
In aerospace, textile material and military affairs etc., and phase-change accumulation energy, the double work(of radiation protection having due to the invention
The characteristics of energy, the invention more particularly to nuclear radiation protection clothing, military architecture etc. need to shield nuclear radiation and need certain store up
The technical field of thermal energy power.
Background technology
In recent years, due to energy shortage and using a series of problems caused by fossil fuel, seek regenerative resource at
For the focus of people.Phase-change material can be absorbed or be discharged in phase transition process as a kind of energy-saving and environment-friendly energy storage material
A large amount of latent heat, to attract the interest of people.And organic phase change material, especially paraffin class, due to its transition temperature range
Extensively, heat storage capacity is strong, and the advantages of without supercooling, therefore can be widely applied to space flight, building, clothes, military affairs etc..But
If since this kind of solid-liquid phase change material will be leaked without processing with regard to application, and they also have the disadvantages such as thermal conductivity is low,
To limit their business application, it is therefore desirable to be coated to phase-change material using microcapsules technology.
Different types of shell has different application directions, and in recent years, there are many about macromolecule organic shell and nothing
The document report and technology of the phase-change microcapsule technology of preparing of casing body disclose.The patent document of Publication No. CN106520078A
Disclose it is a kind of using inorganic material as the preparation method of the microcapsules of storing energy through phase change of wall material, using inorganic material calcium carbonate as wall material,
Using stearic acid as core material, core material stearic acid, emulsifier, calcium chloride and deionized water are added to the container, stirring keeps core material stearic
Acid forms stable emulsification system in emulsifier；Sodium carbonate liquor is slowly dropped in emulsification system, inorganic material is obtained
For the microcapsules of storing energy through phase change of wall material.Although effectively overcoming organic wall material by inorganic wall material phase-change microcapsule prepared by this method
, there is the features such as nontoxic, fire-retardant in the shortcomings of irritation and toxicity of reaction monomers, but its thermal conductance is inadequate, in use
Leakage problem is serious.
The preparation method for the phase-change microcapsule reported be not directed to can phase-change accumulation energy but also radiation proof phase transformation it is micro-
Capsule.Organic solid-liquid phase change material has higher enthalpy and without surfusion as phase-change microcapsule core material in the present invention.
And shell of the lead tungstate as phase-change microcapsule, protective effect not only is played to core material, increases the thermal conductivity of material, is solved
Organic phase change material thermal conductivity low problem, lead tungstate shell also have Study On The Radioprotective.
Invention content
It is excellent it is an object of the invention to solve at least the above and/or defect, and provide at least to will be described later
Point.
In order to realize these purposes and other advantages according to the present invention, a kind of lead tungstate shell phase-change microcapsule is provided
Preparation method, include the following steps：
Step 1: by weight, by 3~6 parts of phase-change materials, 1~2 portion of citrate, 25~35 parts a concentration of 1.5~
The emulsifier solution of 3.5wt% and 40~50 parts of deionized water mixing, it is liquid core material to be melted under 60~80 DEG C of waters bath with thermostatic control,
Emulsification, obtains phase change material emulsion；
Step 2: by weight, the lead salt solution that 60~70 parts of mass fractions are 6~7% is taken to instill 60~80 DEG C of phase
Become in material emulsion, stir 2~5 hours under the rotating speed of 600~900r/min, then by 55~65 parts of mass fractions for 5~
6% tungstate solution instills phase change material emulsion, is stirred 6~9 hours under the rotating speed of 200~400r/min, lead salt and tungsten
Hydrochlorate generates lead tungstate by precipitation reaction and is deposited on phase-change material emulsion droplet surface, forms the shell of cladding core material；
Step 3: the system after step 2 is reacted is cooled to room temperature, phase-change microcapsule is taken out, is washed with deionized,
Drying, obtains lead tungstate shell phase-change microcapsule.
Preferably, the phase-change material is organic solid-liquid phase change material comprising in alkane, aliphatic acid, aliphatic ester
One or more of combinations.
Preferably, organic solid-liquid phase change material is paraffin or stearic acid.
Preferably, the emulsifier solution is styrene-maleic anhydride copolymer, lauryl sodium sulfate, dodecane
The combination of one or more of base benzene sulfonic acid sodium salt, stearic acid solution；The citrate is sodium citrate, calcium citrate, lemon
Any one in lemon acid zinc, potassium citrate.
Preferably, in the step 1, the condition of emulsification is：It is emulsified using high-shear emulsion machine, high-shear emulsion machine
5000~20000r/min of rotating speed, time are 1~10min；In the step 2, lead salt solution instills the speed of phase change material emulsion
Degree is 0.01~0.03mL/s；The speed that tungstate solution instills phase change material emulsion is 0.003~0.008mL/s.
Preferably, the lead salt solution is any one in acetic acid lead solution, lead nitrate solution, chlorination lead solution.
Preferably, the tungstate solution is any one in sodium tungstate solution, ammonium tungstate solution, wolframic acid calcium solution
Kind.
Preferably, the process in the step 2 replaces with：By weight, it is 3.5 to take 100~120 parts of mass fractions
~4.5% lead salt solution instills in 60~80 DEG C of phase change material emulsion, and 2~5 are stirred under the rotating speed of 600~900r/min
Hour, then phase change material emulsion is placed in the container with stainless steel nozzle in Elecstrostatic spraying apparatus, using high voltage power supply
It applies the voltage on stainless steel nozzle, phase change material emulsion is ejected into and fills the tungsten that 55~65 parts of mass fractions are 5~6%
In the reception device of acid salt solution, stirred 3~5 hours under the rotating speed of 200~400r/min, lead salt and tungstates pass through precipitation
Reaction generates lead tungstate and is deposited on phase-change material emulsion droplet surface, forms the shell of cladding core material；The jet strip of the electric injection device
Part is：Environment temperature be 50~60 DEG C, reception device between nozzle at a distance from be 5~10cm, flow be 10~20mL/h, voltage
Internal diameter for 5~10kV, stainless steel nozzle is 0.8~1.6mm.
Preferably, further include being passed through nitrogen in the tungstate solution of reception device；The Ventilation Rate of the nitrogen is
100~150mL/min；System after step 2 is reacted is added in stainless steel spherical container, while the deionization of equivalent is added
Then spherical container is placed on four axis bevellers by water, open four axis bevellers, drives the randomly rotation 30 of stainless steel spherical container
~45min, then takes out phase-change microcapsule, is washed with deionized, and drying obtains lead tungstate shell phase-change microcapsule；It is described
The feed inlet of stainless steel spherical container is sealed by threaded cap, and threaded cap is neat with the surface of stainless steel spherical container after being tightly connected
It is flat；The shaft rotating speed of the four axis beveller is 100~150rpm, and stochastic transition frequency is 30~60s.
The present invention also provides a kind of lead tungstate shell phase-change microcapsule prepared such as above-mentioned preparation method, the lead tungstates
Shell phase-change microcapsule is using organic solid-liquid phase change material as core material, and using lead tungstate as wall material, and it is with phase-change accumulation energy and radiation
Safeguard function.
In the step two of the present invention, into phase change material emulsion, acetic acid lead solution of the addition with cation, makes free
Lead ion occurs electrostatic interaction with phase-change material emulsion droplet and is combined together, and in the process, carries out continuing stirring to solution；It drips again
The sodium tungstate solution of precipitation can be occurred with lead ion by adding, and mixing speed should suitably slow down in the process, and reaction is made to generate
Lead tungstate particle can uniformly be deposited on phase-change material emulsion droplet.
The present invention is using wolframic acid lead material as wall material, and using organic solid-liquid phase change material as core material, anion emulsifier is by core material
Emulsification is surrounded, the Pb in the lead acetate of addition2+It is adsorbed in around emulsifier by attractive coulombic force due to positively charged, is added again at this time
Enter sodium tungstate, WO4 2-With Pb2+Reaction generates PbWO4And core surfaces are deposited on, to be made using wolframic acid lead material as wall material
Microcapsules of storing energy through phase change.
The citrate of the present invention plays the role of stable pH, and lead tungstate crystallization is made soon not formed very much.
The present invention includes at least following advantageous effect：The preparation method of phase-change microcapsule of the present invention is due to using ring
It is wall material to protect the good inorganic material lead tungstate of nontoxic, at low cost and thermal conductivity, uses organic solid-liquid phase change material for core material,
Therefore the lead tungstate shell phase-change microcapsule prepared solves the problems, such as leakage, phase separation and the supercooling of phase-change material and thermal conductivity
The not high technical problem of rate.Meanwhile the shielding gamma-radiation that has of lead tungstate shell and paraffin phase change material and neutron ability,
The lead tungstate shell phase-change microcapsule is set to have phase-change accumulation energy and radiation protection difunctional.
Part is illustrated to embody by further advantage, target and the feature of the present invention by following, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Description of the drawings：
Fig. 1 is mass attenuation of the phase-change microcapsule of the preparation of the embodiment of the present invention 2~4 under different gamma radiation energies
Coefficient；
Fig. 2 is the scanning electron microscope (SEM) photograph of phase-change microcapsule prepared by the embodiment of the present invention 1；
Fig. 3 is the thermal analysis curve of phase-change microcapsule prepared by the embodiment of the present invention 2；
Fig. 4 is the percolation ratio empirical curve of phase-change microcapsule prepared by the embodiment of the present invention 2~4.
Specific implementation mode：
Present invention will be described in further detail below with reference to the accompanying drawings, to enable those skilled in the art with reference to specification text
Word can be implemented according to this.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more
The presence or addition of a other elements or combinations thereof.
Embodiment 1：
A kind of preparation method of lead tungstate shell phase-change microcapsule, includes the following steps：
Step 1: by the anion surfactant benzene second of 5g stearic acid, 1.6g sodium citrates, a concentration of 2wt% of 32mL
Alkene-copolymer-maleic anhydride solution and the mixing of 40mL deionized waters, it is liquid core material to be melted under 70 DEG C of waters bath with thermostatic control, using height
Emulsification pretreatment machine emulsifies, and high-shear emulsion machine rotating speed 10000r/min, time 3min obtain phase change material emulsion；
Step 2: taking 4.17g lead acetates and 3.62g sodium tungstates, 60mL deionized water dissolvings are separately added at solution, by vinegar
Lead plumbate solution is instilled with the speed of 0.02mL/s in 70 DEG C of phase change material emulsion, is stirred 3 hours under the rotating speed of 800r/min,
Then sodium tungstate solution is instilled into phase change material emulsion with the speed of 0.005mL/s, it is small that 8 is stirred under the rotating speed of 300r/min
When, lead salt and tungstates generate lead tungstate by precipitation reaction and are deposited on phase-change material emulsion droplet surface, form the shell of cladding core material
Body；
Step 3: the system after step 2 is reacted is cooled to room temperature, phase-change microcapsule is taken out, is washed with deionized,
40 DEG C of drying, obtain lead tungstate shell phase-change microcapsule；
The percolation ratio of phase-change microcapsule prepared by the embodiment when testing 1200min is 6.12%；Fig. 2 shows the realities
Apply the scanning electron microscope (SEM) photograph of the phase-change microcapsule of example preparation.
Embodiment 2：
A kind of preparation method of lead tungstate shell phase-change microcapsule, includes the following steps：
Step 1: by 5g paraffin, the anion surfactant styrene-of 1.6g sodium citrates, a concentration of 2wt% of 32mL
Copolymer-maleic anhydride solution and the mixing of 40mL deionized waters, it is liquid core material to be melted under 70 DEG C of waters bath with thermostatic control, is cut using height
Mulser emulsification is cut, high-shear emulsion machine rotating speed 10000r/min, time 3min obtain phase change material emulsion；
Step 2: taking 4.17g lead acetates and 3.62g sodium tungstates, 60mL deionized water dissolvings are separately added at solution, by vinegar
Lead plumbate solution is instilled with the speed of 0.02mL/s in 70 DEG C of phase change material emulsion, is stirred 3 hours under the rotating speed of 800r/min,
Then sodium tungstate solution is instilled into phase change material emulsion with the speed of 0.005mL/s, it is small that 8 is stirred under the rotating speed of 300r/min
When, lead salt and tungstates generate lead tungstate by precipitation reaction and are deposited on phase-change material emulsion droplet surface, form the shell of cladding core material
Body；
Step 3: the system after step 2 is reacted is cooled to room temperature, phase-change microcapsule is taken out, is washed with deionized,
40 DEG C of drying, obtain lead tungstate shell phase-change microcapsule；Phase-change microcapsule prepared by the embodiment is surveyed through differential scanning calorimetry
Fixed, as shown in figure 3, its potential heat value is 80.64J/g, phase transition temperature is 43.13 DEG C.
Embodiment 3：
A kind of preparation method of lead tungstate shell phase-change microcapsule, includes the following steps：
Step 1: by 5g paraffin, the anion surfactant styrene-of 1.6g sodium citrates, a concentration of 2wt% of 32mL
Copolymer-maleic anhydride solution and the mixing of 40mL deionized waters, it is liquid core material to be melted under 70 DEG C of waters bath with thermostatic control, is cut using height
Mulser emulsification is cut, high-shear emulsion machine rotating speed 10000r/min, time 3min obtain phase change material emulsion；
Step 2: taking 2.37g lead acetates and 1.82g sodium tungstates, 60mL deionized water dissolvings are separately added at solution, by vinegar
Lead plumbate solution is instilled with the speed of 0.02mL/s in 70 DEG C of phase change material emulsion, is stirred 3 hours under the rotating speed of 800r/min,
Then sodium tungstate solution is instilled into phase change material emulsion with the speed of 0.005mL/s, it is small that 8 is stirred under the rotating speed of 300r/min
When, lead salt and tungstates generate lead tungstate by precipitation reaction and are deposited on phase-change material emulsion droplet surface, form the shell of cladding core material
Body；
Step 3: the system after step 2 is reacted is cooled to room temperature, phase-change microcapsule is taken out, is washed with deionized,
40 DEG C of drying, obtain lead tungstate shell phase-change microcapsule.
Embodiment 4：
A kind of preparation method of lead tungstate shell phase-change microcapsule, includes the following steps：
Step 1: by 5g paraffin, the anion surfactant styrene-of 1.6g sodium citrates, a concentration of 2wt% of 32mL
Copolymer-maleic anhydride solution and the mixing of 40mL deionized waters, it is liquid core material to be melted under 70 DEG C of waters bath with thermostatic control, is cut using height
Mulser emulsification is cut, high-shear emulsion machine rotating speed 10000r/min, time 3min obtain phase change material emulsion；
Step 2: taking 7.79g lead acetates and 7.24g sodium tungstates, 60mL deionized water dissolvings are separately added at solution, by vinegar
Lead plumbate solution is instilled with the speed of 0.02mL/s in 70 DEG C of phase change material emulsion, is stirred 3 hours under the rotating speed of 800r/min,
Then sodium tungstate solution is instilled into phase change material emulsion with the speed of 0.005mL/s, it is small that 8 is stirred under the rotating speed of 300r/min
When, lead salt and tungstates generate lead tungstate by precipitation reaction and are deposited on phase-change material emulsion droplet surface, form the shell of cladding core material
Body；
Step 3: the system after step 2 is reacted is cooled to room temperature, phase-change microcapsule is taken out, is washed with deionized,
40 DEG C of drying, obtain lead tungstate shell phase-change microcapsule.
Embodiment 5：
A kind of preparation method of lead tungstate shell phase-change microcapsule, includes the following steps：
Step 1: by 5g paraffin, the anion surfactant dodecane of 1.6g potassium citrates, a concentration of 2wt% of 35mL
Base benzene sulfonic acid sodium salt solution and the mixing of 40mL deionized waters, it is liquid core material to be melted under 70 DEG C of waters bath with thermostatic control, using high shear breast
Change machine emulsifies, and high-shear emulsion machine rotating speed 10000r/min, time 3min obtain phase change material emulsion；
Step 2: taking 4.17g lead acetates and 3.62g sodium tungstates, 60mL deionized water dissolvings are separately added at solution, by vinegar
Lead plumbate solution is instilled with the speed of 0.02mL/s in 70 DEG C of phase change material emulsion, is stirred 3 hours under the rotating speed of 800r/min,
Then sodium tungstate solution is instilled into phase change material emulsion with the speed of 0.005mL/s, it is small that 8 is stirred under the rotating speed of 300r/min
When, lead salt and tungstates generate lead tungstate by precipitation reaction and are deposited on phase-change material emulsion droplet surface, form the shell of cladding core material
Body；
Step 3: the system after step 2 is reacted is cooled to room temperature, phase-change microcapsule is taken out, is washed with deionized,
40 DEG C of drying, obtain lead tungstate shell phase-change microcapsule.
The percolation ratio of phase-change microcapsule prepared by the embodiment when testing 1200min is 5.28%.
Embodiment 6：
A kind of preparation method of lead tungstate shell phase-change microcapsule, includes the following steps：
Step 1: by 5g paraffin, the anion surfactant dodecane of 1.6g zinc citrates, a concentration of 3wt% of 30mL
Base metabisulfite solution and the mixing of 40mL deionized waters, it is liquid core material to be melted under 70 DEG C of waters bath with thermostatic control, using high-shear emulsifying
Machine emulsifies, and high-shear emulsion machine rotating speed 10000r/min, time 3min obtain phase change material emulsion；
Step 2: taking 4.17g lead acetates and 3.62g sodium tungstates, 60mL deionized water dissolvings are separately added at solution, by vinegar
Lead plumbate solution is instilled with the speed of 0.02mL/s in 70 DEG C of phase change material emulsion, is stirred 3 hours under the rotating speed of 800r/min,
Then sodium tungstate solution is instilled into phase change material emulsion with the speed of 0.005mL/s, it is small that 8 is stirred under the rotating speed of 300r/min
When, lead salt and tungstates generate lead tungstate by precipitation reaction and are deposited on phase-change material emulsion droplet surface, form the shell of cladding core material
Body；
Step 3: the system after step 2 is reacted is cooled to room temperature, phase-change microcapsule is taken out, is washed with deionized,
40 DEG C of drying, obtain lead tungstate shell phase-change microcapsule.
The percolation ratio of phase-change microcapsule prepared by the embodiment when testing 1200min is 5.58%.
Embodiment 7：
Process in the step 2 replaces with：It takes 7.79g lead acetates to be added in 100mL deionized waters and is dissolved into solution,
Then acetic acid lead solution is instilled in 70 DEG C of phase change material emulsion with the speed of 0.02mL/s, is stirred under the rotating speed of 800r/min
It mixes 3 hours, then phase change material emulsion is placed in the container with stainless steel nozzle in Elecstrostatic spraying apparatus, using high-voltage electricity
Source applies the voltage on stainless steel nozzle, and phase change material emulsion is ejected into the reception device for filling sodium tungstate solution,
It is stirred 5 hours under the rotating speed of 300r/min, lead salt and tungstates generate lead tungstate by precipitation reaction and be deposited on phase-change material breast
Surface is dripped, the shell of cladding core material is formed；The injection conditions of the electric injection device is：Environment temperature be 60 DEG C, reception device with
Distance between nozzle is 10cm, flow 15mL/h, voltage 8kV, and the internal diameter of stainless steel nozzle is 1.2mm；The sodium tungstate
The preparation of solution is added in 60mL deionized waters using 7.24g sodium tungstates and is obtained；The micro- glue of phase transformation is carried out using Elecstrostatic spraying apparatus
The preparation of capsule further enhances the surface reaction forces that wall material deposition is supported on core material, reduces the phase-change microcapsule of preparation
Percolation ratio.
Remaining technological parameter and process with it is identical in embodiment 4.
The percolation ratio of phase-change microcapsule prepared by the embodiment when testing 1200min is 3.25%.
Embodiment 8：
Process in the step 2 replaces with：It takes 7.79g lead acetates to be added in 100mL deionized waters and is dissolved into solution,
Then acetic acid lead solution is instilled in 70 DEG C of phase change material emulsion with the speed of 0.03mL/s, is stirred under the rotating speed of 800r/min
It mixes 3 hours, then phase change material emulsion is placed in the container with stainless steel nozzle in Elecstrostatic spraying apparatus, using high-voltage electricity
Source applies the voltage on stainless steel nozzle, and phase change material emulsion is ejected into the reception device for filling sodium tungstate solution,
It is stirred 5 hours under the rotating speed of 300r/min, lead salt and tungstates generate lead tungstate by precipitation reaction and be deposited on phase-change material breast
Surface is dripped, the shell of cladding core material is formed；The injection conditions of the electric injection device is：Environment temperature be 50 DEG C, reception device with
Distance between nozzle is 5cm, flow 10mL/h, voltage 10kV, and the internal diameter of stainless steel nozzle is 1.2mm；The sodium tungstate
The preparation of solution is added in 60mL deionized waters using 7.24g sodium tungstates and is obtained；
Remaining technological parameter and process with it is identical in embodiment 4.
The percolation ratio of phase-change microcapsule prepared by the embodiment when testing 1200min is 3.18%.
Embodiment 9：
Further include being passed through nitrogen in the tungstate solution of reception device；The Ventilation Rate of the nitrogen is 100mL/
min；The process of the step 3 is：System after step 2 is reacted is added in stainless steel spherical container, while equivalent is added
Deionized water, then spherical container is placed on four axis bevellers, open four axis bevellers, drive stainless steel spherical container without
Rule rotation 45min, then takes out phase-change microcapsule, is washed with deionized, dry, obtain lead tungstate shell phase-change microcapsule；
The feed inlet of the stainless steel spherical container is sealed by threaded cap, the table after threaded cap sealed connection with stainless steel spherical container
Face flushes；The shaft rotating speed of the four axis beveller is 100rpm, and stochastic transition frequency is 30s.It is ground using random four axis of four axis
It grinds instrument and carries spherical container, realize the random rotation solidification in spherical container, the method overcome the fixations in traditional flow field to take
To problem, no fixed orientation rotation solidification is realized, the concentricization power of phase-change microcapsule is increased considerably, reduces Flow Field outside production
Raw asphericalization, increases the spheroidization degree of phase-change microcapsule, while further reduced the phase-change microcapsule of preparation
Percolation ratio.
Remaining technological parameter and process with it is identical in embodiment 7.
The percolation ratio of phase-change microcapsule prepared by the embodiment when testing 1200min is 2.45%.
Embodiment 10：
Further include being passed through nitrogen in the tungstate solution of reception device；The Ventilation Rate of the nitrogen is 120mL/
min；The process of the step 3 is：System after step 2 is reacted is added in stainless steel spherical container, while equivalent is added
Deionized water, then spherical container is placed on four axis bevellers, open four axis bevellers, drive stainless steel spherical container without
Rule rotation 30min, then takes out phase-change microcapsule, is washed with deionized, dry, obtain lead tungstate shell phase-change microcapsule；
The feed inlet of the stainless steel spherical container is sealed by threaded cap, the table after threaded cap sealed connection with stainless steel spherical container
Face flushes；The shaft rotating speed of the four axis beveller is 120rpm, and stochastic transition frequency is 60s.
Remaining technological parameter and process with it is identical in embodiment 8, the phase-change microcapsule which prepares is in reality
Percolation ratio when testing 1200min is 2.32%.
Gamma ray shielding test is carried out using the lead tungstate shell phase-change microcapsule prepared in embodiment 2~4, using tool
There are two types of the high-purity Germanium gamma spectrometers of gamma emitter to measure gamma radiation shielding absorption, and the gamma emitter includes mixed
The Eu of conjunction-155And Na-22(E~86keV, 105keV, 511keV and 1274keV).The decaying behavior of high-energy photon can use following formula
Simply indicate：I (t)=I0e-μmρt, wherein I (t) and I0It is the intensity of transmission and incident radiation respectively, μm is mass attenuation system
Number depends on energy and material, and ρ is the bulk density (g/cm of composite material3), t is the thickness (cm) of composite material, table 1 and figure
1 shows mass attentuation coefficient of each sample under different gamma ray radiation energy；
Table 1
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Energy (MeV) | μ | μ | μ |
| 0.086 | 5.966274 | 2.710287 | 1.862252 |
| 0.105 | 10.70214 | 7.127126 | 5.483841 |
| 0.51 | 0.175162 | 0.270322 | 0.208931 |
| 1.274 | 0.018975 | 0.03741 | 0.17386 |
Mass attentuation coefficient is the important parameter for illustrating gamma-rays attenuation coefficient.As shown in Table 1, at low energies, various kinds
Product show higher mass attentuation coefficient, i.e., gamma ray shielding properties at low energies is relatively good, and with micro- glue
The ratio of lead tungstate shell increases and increases in capsule；This is related with the mass fraction shared by lead tungstate in microcapsules；But in height
Under the gamma ray of energy, Decay Rate is poor, i.e., poor to gamma ray shielding properties.
Percolation ratio test experiments are carried out to phase-change microcapsule prepared by the embodiment 2~4, percolation ratio test experiments are true
It is carried out in empty drying box, each formula takes 3 samples, weighs, as initial mass, when being then placed in one section of vacuum drying chamber
Between, it takes out, dries surface paraffin, be cooled to room temperature and weigh, so carry out repetition test, calculate the percolation ratio of phase-change microcapsule.
The test result of percolation ratio is as shown in table 2 and Fig. 4, it can be seen that the leakage of phase-change microcapsule prepared by the embodiment of the present invention 2~4
Rate is gradually stablized after 300min, and in 1200min, phase-change microcapsule percolation ratio prepared by embodiment 2 is 6.16%；Embodiment
The 3 phase-change microcapsule percolation ratios prepared are 7.29%；Phase-change microcapsule percolation ratio prepared by embodiment 4 is 4.74%.
Table 2
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and legend shown and described herein.
Claims (10)
1. a kind of preparation method of lead tungstate shell phase-change microcapsule, which is characterized in that include the following steps：
Step 1: by weight, by 3~6 parts of phase-change materials, 1~2 portion of citrate, 25~35 parts a concentration of 1.5~
The emulsifier solution of 3.5wt% and 40~50 parts of deionized water mixing, form liquid core material, breast under 60~80 DEG C of waters bath with thermostatic control
Change, obtains phase change material emulsion；
Step 2: by weight, the lead salt solution that 60~70 parts of mass fractions are 6~7% is taken to instill 60~80 DEG C of phase transformation material
Expect in lotion, is stirred under the rotating speed of 600~900r/min 2~5 hours, be then 5~6% by 55~65 parts of mass fractions
Tungstate solution instills phase change material emulsion, is stirred 6~9 hours under the rotating speed of 200~400r/min, and lead salt and tungstates are logical
It crosses precipitation reaction generation lead tungstate and is deposited on phase-change material emulsion droplet surface, form the shell of cladding core material；
Step 3: the system after step 2 is reacted is cooled to room temperature, phase-change microcapsule is taken out, is washed with deionized, dried,
Obtain lead tungstate shell phase-change microcapsule.
2. the preparation method of lead tungstate shell phase-change microcapsule as described in claim 1, which is characterized in that the phase-change material
For organic solid-liquid phase change material comprising one or more of combination in alkane, aliphatic acid, aliphatic ester.
3. the preparation method of lead tungstate shell phase-change microcapsule as claimed in claim 2, which is characterized in that it is described it is organic it is solid-
Liquid phase-change material is paraffin or stearic acid.
4. the preparation method of lead tungstate shell phase-change microcapsule as described in claim 1, which is characterized in that the emulsifier is molten
Liquid is one kind in styrene-maleic anhydride copolymer, lauryl sodium sulfate, neopelex, stearic acid solution
Or several combination；The citrate is any one in sodium citrate, calcium citrate, zinc citrate, potassium citrate.
5. the preparation method of lead tungstate shell phase-change microcapsule as described in claim 1, which is characterized in that the step 1
In, the condition of emulsification is：It is emulsified using high-shear emulsion machine, high-shear emulsion machine 5000~20000r/min of rotating speed, the time 1
~10min；In the step 2, the speed that lead salt solution instills phase change material emulsion is 0.01~0.03mL/s；Tungstates is molten
The speed that drop enters phase change material emulsion is 0.003~0.008mL/s.
6. the preparation method of lead tungstate shell phase-change microcapsule as described in claim 1, which is characterized in that the lead salt solution
For any one in acetic acid lead solution, lead nitrate solution, chlorination lead solution.
7. the preparation method of lead tungstate shell phase-change microcapsule as described in claim 1, which is characterized in that the tungstates is molten
Liquid is any one in sodium tungstate solution, ammonium tungstate solution, wolframic acid calcium solution.
8. the preparation method of lead tungstate shell phase-change microcapsule as described in claim 1, which is characterized in that in the step 2
Process replace with：By weight, the lead salt solution that 100~120 parts of mass fractions are 3.5~4.5% is taken to instill 60~80 DEG C
Phase change material emulsion in, stir 2~5 hours, be then placed in phase change material emulsion quiet under the rotating speed of 600~900r/min
It in the container with stainless steel nozzle in electrical spraying device, is applied the voltage on stainless steel nozzle using high voltage power supply, by phase
Become material emulsion and be ejected into and fills 55~65 parts of mass fractions as in the reception device of 5~6% tungstate solution, 200~
It is stirred 3~5 hours under the rotating speed of 400r/min, lead salt and tungstates generate lead tungstate by precipitation reaction and be deposited on phase-change material
Emulsion droplet surface forms the shell of cladding core material；The injection conditions of the electric injection device is：Environment temperature is 50~60 DEG C, is received
Device between nozzle at a distance from be 5~10cm, flow is 10~20mL/h, and voltage is 5~10kV, and the internal diameter of stainless steel nozzle is
0.8~1.6mm.
9. the preparation method of lead tungstate shell phase-change microcapsule as claimed in claim 8, which is characterized in that further include connecing
It is passed through nitrogen in the tungstate solution of receiving apparatus；The Ventilation Rate of the nitrogen is 100~150mL/min；Step 2 is reacted
System afterwards is added in stainless steel spherical container, while the deionized water of equivalent is added, and spherical container, which is then placed in four axis, grinds
It grinds on instrument, opens four axis bevellers, drive stainless steel spherical container randomly 30~45min of rotation, then take out phase-change microcapsule,
It is washed with deionized, dries, obtain lead tungstate shell phase-change microcapsule；The feed inlet of the stainless steel spherical container passes through spiral shell
Line lid seals, and threaded cap flushes after being tightly connected with the surface of stainless steel spherical container；The shaft rotating speed of the four axis beveller
For 100~150rpm, stochastic transition frequency is 30~60s.
10. lead tungstate shell phase-change microcapsule prepared by a kind of preparation method as described in any one of claim 1~9, feature
It is, the lead tungstate shell phase-change microcapsule is using organic solid-liquid phase change material as core material, and using lead tungstate as wall material, and it has
There are phase-change accumulation energy and radiation protection function.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109177396A (en) * | 2018-09-17 | 2019-01-11 | 浙江三元电子科技有限公司 | A kind of protection composite material and preparation method |
| CN110359151A (en) * | 2019-07-09 | 2019-10-22 | 西南科技大学 | One kind having temperature controlling function nuclear radiation protection yarn and preparation method thereof |
| CN112126414A (en) * | 2020-10-12 | 2020-12-25 | 西南科技大学 | Method for preparing phase-change microcapsule by hydrothermal method |
| CN114525110A (en) * | 2020-10-31 | 2022-05-24 | 中国石油化工股份有限公司 | Inorganic capsule wall phase change microcapsule and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014105301A (en) * | 2012-11-29 | 2014-06-09 | Riso Kagaku Corp | Capsule type heat radiation heat storage material and production method of the same, and production apparatus of capsule type heat radiation heat storage material |
| CN104900282A (en) * | 2015-04-14 | 2015-09-09 | 西南科技大学 | Gamma radiation protective clothing preparing method |
| US20160209722A1 (en) * | 2010-04-30 | 2016-07-21 | View, Inc. | Electrochromic devices |
| CN110359151A (en) * | 2019-07-09 | 2019-10-22 | 西南科技大学 | One kind having temperature controlling function nuclear radiation protection yarn and preparation method thereof |
-
2018
- 2018-04-27 CN CN201810389487.5A patent/CN108441175B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160209722A1 (en) * | 2010-04-30 | 2016-07-21 | View, Inc. | Electrochromic devices |
| JP2014105301A (en) * | 2012-11-29 | 2014-06-09 | Riso Kagaku Corp | Capsule type heat radiation heat storage material and production method of the same, and production apparatus of capsule type heat radiation heat storage material |
| CN104900282A (en) * | 2015-04-14 | 2015-09-09 | 西南科技大学 | Gamma radiation protective clothing preparing method |
| CN110359151A (en) * | 2019-07-09 | 2019-10-22 | 西南科技大学 | One kind having temperature controlling function nuclear radiation protection yarn and preparation method thereof |
Non-Patent Citations (7)
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109177396A (en) * | 2018-09-17 | 2019-01-11 | 浙江三元电子科技有限公司 | A kind of protection composite material and preparation method |
| CN110359151A (en) * | 2019-07-09 | 2019-10-22 | 西南科技大学 | One kind having temperature controlling function nuclear radiation protection yarn and preparation method thereof |
| CN112126414A (en) * | 2020-10-12 | 2020-12-25 | 西南科技大学 | Method for preparing phase-change microcapsule by hydrothermal method |
| CN112126414B (en) * | 2020-10-12 | 2021-06-25 | 西南科技大学 | Method for preparing phase-change microcapsule by hydrothermal method |
| CN114525110A (en) * | 2020-10-31 | 2022-05-24 | 中国石油化工股份有限公司 | Inorganic capsule wall phase change microcapsule and preparation method and application thereof |
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