CN111154033A - Gel type ice and snow material with adjustable solidification temperature and transmittance and preparation method thereof - Google Patents

Gel type ice and snow material with adjustable solidification temperature and transmittance and preparation method thereof Download PDF

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Publication number
CN111154033A
CN111154033A CN202010041124.XA CN202010041124A CN111154033A CN 111154033 A CN111154033 A CN 111154033A CN 202010041124 A CN202010041124 A CN 202010041124A CN 111154033 A CN111154033 A CN 111154033A
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solidification temperature
snow
transmittance
acrylamide
type ice
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张凯
渐南南
程杨洋
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Beijing Institute of Technology BIT
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Beijing Institute of Technology BIT
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/24—Materials not provided for elsewhere for simulating ice or snow
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A gel type ice and snow material with adjustable solidification temperature and transmittance and a preparation method thereof are disclosed, which specifically comprise the following steps: firstly, preparing an acrylamide ice and snow material by using an acrylamide polymerization monomer, a cross-linking agent, an initiator, a catalyst, a solidification temperature and transmittance regulator as raw materials; and secondly, adopting sodium alginate, a solubilizer, a soluble divalent/trivalent metal ion salt, a crosslinking speed regulator, a plasticizer, a gelling agent and a solidification temperature and transmittance regulator as raw materials, and obtaining the sodium alginate gel type ice and snow material through ion crosslinking. The invention can realize the regulation and control of the solidification temperature of the gel type ice and snow material in a wider interval by blending the raw material components, and the synthesized material has the characteristics of good formability and easy processing.

Description

Gel type ice and snow material with adjustable solidification temperature and transmittance and preparation method thereof
Technical Field
The invention relates to the field of new material preparation and processing, in particular to a gel type ice and snow material with adjustable solidification temperature and transmittance and a preparation method thereof.
Background
The crystal ice is clear, and the snow is white and moist, so that the ice and snow culture has unique charm, and people are happy in colorful ice and snow world. However, the life of ice and snow works such as ice carving and snow carving is short and fragile, because the ice and snow are melted into water due to the rise of the environmental temperature, the original structural form is lost, and the ice and snow works cannot be stored for a long time. Meanwhile, the poor formability and processability of ice and snow make the ice and snow impossible to become a processing material, such as ornaments, souvenirs, ornamental articles, toys and the like, and the ice and snow become a great obstacle to the close integration of the ice and snow with the life of people.
CN104861931A discloses a preparation method of artificial snow, which comprises the steps of preparing pre-sintered pellets from raw materials sequentially through a batching process, a mixing process and a pre-sintering process, and then performing a powder coating process by using the pre-sintered pellets as a magnetic matrix for artificial snow, wherein the powder coating process comprises a primary coating step, a secondary coating step and a varnishing step which are sequentially performed, and after the powder coating process is completed, the molded artificial snow with high coverage rate is prepared. CN106751287A discloses an artificial snowplow, comprising: a plurality of particles of an inorganic salt; and a polymer solution layer which is in a colloid shape and coats the surface of the inorganic salt particles, wherein the polymer solution layer is composed of a water-soluble water-absorbing polymer and an aqueous solvent.
However, none of the above techniques can achieve no water separation and no water loss after the artificial snow material is heated and melted, and still maintain the original shape and ice permeability.
Disclosure of Invention
Based on the requirements, the invention provides a gel type ice and snow material with adjustable solidification temperature and transmittance and a preparation method thereof, the gel type ice and snow material presents a visual effect of snow when being solidified, can effectively lock water after being melted, presents the light transmittance of ice and keeps the original structural shape; and the solidification temperature can be changed in a wide temperature range by blending the components, so that the application requirements of different ice and snow works on light transmission and temperature can be met.
The specific technical scheme of the invention is as follows:
an acrylamide gel type ice and snow material with adjustable solidification temperature and transmittance is prepared from the following raw materials: acrylamide polymerization monomers, a cross-linking agent, an initiator, a catalyst, a solidification temperature and transmittance regulator and water; the mass ratio of the components is 5-25: 0.02-0.1: 0.01-0.2: 0.001-0.02: 0.1-30: 100.
Preferably, the acrylamide-based polymerized monomer is selected from one or more of acrylamide, methacrylamide, N-isopropylacrylamide, N-phenylacrylamide, N-t-butylacrylamide and diacetone acrylamide.
Preferably, the crosslinking agent is selected from one or more of N, N-methylene bisacrylamide, N-methylol acrylamide, diacetone acrylamide, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
Preferably, the initiator is a thermal initiator or a photoinitiator. The thermal initiator is selected from one or more of potassium persulfate, sodium persulfate and ammonium persulfate; the photoinitiator is one or more selected from 2-ketoglutaric acid and 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone.
Preferably, the catalyst is tetramethylethylenediamine.
Preferably, the solidification temperature and transmittance regulator is selected from one or more of inorganic salts and organic alcohols. Wherein the inorganic salt is one or more of sodium chloride, calcium chloride, lithium chloride, potassium chloride and magnesium chloride; the organic alcohol is one or two of ethylene glycol and glycerol.
The preparation method of the acrylamide gel type ice and snow material with adjustable solidification temperature and transmittance comprises the following steps:
(1) and dissolving the acrylamide polymerization monomer, the cross-linking agent, the initiator, the catalyst, the solidification temperature and transmittance regulator in water according to the mass ratio, fully stirring until the acrylamide polymerization monomer, the cross-linking agent, the initiator, the catalyst, the solidification temperature and the transmittance regulator are completely dissolved, and performing vacuum defoaming treatment to obtain the gel-type ice and snow precursor solution.
(2) Injecting the precursor solution in the step (1) into a container or a mold, and covering a glass sheet subjected to surface hydrophobic treatment on the container or the mold; heating or ultraviolet irradiation to completely cure the ice and snow to obtain the acrylamide gel ice and snow.
Preferably, the water in step (1) is selected from one or two of deionized water, tap water, rainwater and snow water, and the volume of the water is 100 ml.
Preferably, the heating temperature in the step (2) is 40-70 ℃, and the heating time is 1.0-3.0 h; the ultraviolet light irradiation wavelength is 365nm, and the irradiation time is 0.5-2.0 h.
A sodium alginate gel type ice and snow material with adjustable solidification temperature and transmittance is prepared from the following raw materials: sodium alginate, a solubilizer, a soluble divalent/trivalent metal ion salt, a crosslinking speed regulator, a plasticizer, a gelling agent, a solidification temperature and transmittance regulator and water, wherein the mass ratio of the raw materials is as follows: 1.0: 2.5-6.5: 0.02-0.5: 0.001-0.5: 0-0.2: 0.05-0.3: 2-10.
Preferably, the solubilizer is selected from one or more of soft sugar, glucose, fructose, maltose, sucrose and lactose.
Preferably, the soluble divalent metal ion salt is selected from one or more of calcium salt, magnesium salt and ferrous salt, the soluble trivalent metal ion salt is selected from one of aluminum salt and iron salt, and the calcium salt is selected from one or more of calcium sulfate, calcium chloride, calcium bromide, calcium iodide, calcium nitrate, calcium formate and calcium acetate.
Preferably, the crosslinking rate modifier is tetrasodium pyrophosphate.
Preferably, the plasticizer is selected from one or more of corn starch, tapioca starch, wheat flour and diatomite.
Preferably, the gelling agent is selected from one or more of xanthan gum, pectin and carrageenan.
Preferably, the solidification temperature and transmittance regulator is selected from one or more of inorganic salts and organic alcohols. Wherein the inorganic salt is selected from one or more of sodium chloride, calcium chloride, lithium chloride, potassium chloride and magnesium chloride; the organic alcohol is one or two of ethylene glycol and glycerol.
A preparation method of a sodium alginate ice and snow material with adjustable solidification temperature and transmittance comprises the following steps: :
(1) fully mixing the sodium alginate, the solubilizer, the soluble divalent/trivalent metal ion salt, the crosslinking speed regulator, the plasticizer and the gelling agent;
(2) dissolving a solidification temperature and transmittance regulator in water to obtain a solidification temperature regulating solution;
(3) dissolving the mixture obtained in the step (1) in the solidification temperature adjusting solution obtained in the step (2), fully stirring until the mixture is completely dissolved, and then carrying out vacuum degassing treatment to obtain a gel type ice and snow precursor solution;
(4) and (4) injecting the precursor solution obtained in the step (3) into a container or a mold, covering a glass sheet subjected to surface hydrophobic treatment on the container or the mold, and curing to obtain the sodium alginate gel type ice and snow material with adjustable solidification temperature and transmittance.
Preferably, the water in step (2) is selected from one or two of deionized water, tap water, rainwater and snow water.
Preferably, the curing time in the step (4) is 5-30 min.
Compared with the prior art, the invention has the following beneficial effects:
(1) the solidification temperature and the transmittance of the ice and snow material prepared by the invention can be adjusted by changing the contents of the solidification temperature and the transmittance regulator in the formula, so that the influence of the environmental temperature on the ice and snow material is weakened, the life cycle of the material is prolonged, and the application scene is expanded.
(2) The gel type ice and snow material prepared by the invention has the characteristic of reversible conversion of ice and snow states, and has the light transmittance of ice before solidification and the whiteness of snow after solidification.
(3) The gel type ice and snow material does not separate water and lose water after being melted and has the processable property. The original structural shape can be still kept after melting, and the material can be used for manufacturing ornaments, souvenirs and the like.
Detailed Description
The present invention is illustrated below with reference to examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited thereto.
Example 1
(1) 3g of polymerized monomer acrylamide, 1.5g of N-isopropyl acrylamide, 0.5g of N-tert-butyl acrylamide, 0.1g of crosslinking agent N, N-methylene bisacrylamide, 0.2g of thermal initiator potassium persulfate, 0.001g of catalyst tetramethylethylenediamine, 8g of solidification temperature and transmittance regulator sodium chloride and 22g of calcium chloride are dissolved in 100g of water, and the mixture is fully stirred until the mixture is completely dissolved and then subjected to vacuum defoaming treatment to prepare the gel type ice and snow material precursor solution.
(2) Injecting the precursor solution in the step (1) into a container or a mold, and capping a glass sheet subjected to surface hydrophobic treatment above the container or the mold; heating to 70 ℃, reacting for 3h, and completely curing to obtain the acrylamide gel type ice and snow material with adjustable solidification temperature and transmittance.
Example 2
(1) 8g of polymerized monomer N-phenyl acrylamide, 17g of diacetone acrylamide, 0.02g of crosslinking agent hydroxypropyl methacrylate, 0.01g of photoinitiator 2-ketoglutaric acid, 0.02g of catalyst tetramethyl ethylenediamine and 0.2g of solidification temperature and transmittance regulator glycerol are dissolved in 100g of water, fully stirred until the components are completely dissolved, and then subjected to vacuum defoaming treatment to obtain the precursor solution of the gel type ice and snow material.
(2) Injecting the precursor solution in the step (1) into a container or a mold, and capping a glass sheet subjected to surface hydrophobic treatment above the container or the mold; and irradiating by adopting ultraviolet light with the wavelength of 365nm for 0.5 hour to completely cure the ice and snow so as to obtain the acrylamide gel type ice and snow material with adjustable solidification temperature and transmittance.
Example 3
(1) According to the mass proportion, 1.0g of sodium alginate, 1.6g of solubilizer soft sugar, 0.9g of cane sugar, 0.35g of soluble divalent metal ion salt calcium sulfate, 0.15g of calcium chloride, 0.002g of crosslinking speed regulator tetrasodium pyrophosphate, 0.2g of plasticizer corn starch, 0.2g of gelling agent xanthan gum, 0.23g of temperature and transmittance regulator sodium chloride and 0.06g of calcium chloride are fully mixed.
(2) Dissolving a solidification temperature and transmittance regulator in 5g of water to obtain a solidification temperature regulating solution;
(3) dissolving the mixed powder particles obtained in the step (1) in the solidification temperature adjusting solution obtained in the step (1), fully stirring until the mixed powder particles are completely dissolved, and then carrying out vacuum degassing treatment to prepare a precursor solution of the gel-type ice and snow material;
(4) and (4) injecting the precursor solution obtained in the step (3) into a container or a mold, covering a glass sheet subjected to surface hydrophobic treatment on the container or the mold, and curing for 5 minutes to obtain the sodium alginate gel type ice and snow material with adjustable solidification temperature and transmittance.
Example 4
(1) According to the mass proportion, 1.0g of sodium alginate, 5.0g of solubilizer glucose, 1.5g of maltose, 0.02g of soluble divalent metal ion salt calcium nitrate, 0.02g of crosslinking speed regulator tetrasodium pyrophosphate, 0.2g of plasticizer wheat flour, 0.2g of gelling agent xanthan gum and 0.05g of temperature and transmittance regulator ethylene glycol are fully mixed.
(2) Dissolving a solidification temperature and transmittance regulator in 10g of water to obtain a solidification temperature regulating solution;
(3) dissolving the mixed powder particles obtained in the step (1) in the solidification temperature adjusting solution obtained in the step (2), fully stirring until the mixed powder particles are completely dissolved, and then performing vacuum degassing treatment to obtain a precursor solution of the gel-type ice and snow material;
(4) and (4) injecting the precursor solution obtained in the step (3) into a container or a mold, covering a glass sheet subjected to surface hydrophobic treatment on the container or the mold, and curing for 30 minutes to obtain the sodium alginate gel type ice and snow material with adjustable solidification temperature and transmittance.
For the purpose of illustration, exemplary embodiments of the invention have been described, but it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope and spirit of the invention as disclosed in the appended claims, and all such changes are intended to fall within the scope of the claims, and the various steps in the various sections and methods of the claimed product may be combined together in any combination. Therefore, the description of the embodiments disclosed in the present invention is not intended to limit the scope of the present invention, but to describe the present invention. Accordingly, the scope of the present invention is not limited by the above embodiments, but is defined by the claims or their equivalents.

Claims (10)

1. The utility model provides an acrylamide gel type ice and snow material of solidification temperature and transmittance adjustable which characterized in that, its preparation raw materials are: acrylamide polymerization monomer, cross-linking agent, initiator, catalyst, solidification temperature and transmittance regulator and water, wherein the mass ratio of the raw materials is as follows: 5-25: 0.02-0.1: 0.01-0.2: 0.001-0.02: 0.1-30: 100.
2. An ice and snow material as claimed in claim 1, wherein: the acrylamide polymerization monomer is one or more of acrylamide, methacrylamide, N-isopropyl acrylamide, N-phenyl acrylamide, N-tert-butyl acrylamide and diacetone acrylamide; the cross-linking agent is one or more of N, N-methylene bisacrylamide, N-hydroxymethyl acrylamide, diacetone acrylamide, hydroxyethyl methacrylate and hydroxypropyl methacrylate; the initiator is a thermal initiator or a photoinitiator, and the thermal initiator is one or more of potassium persulfate, sodium persulfate and ammonium persulfate; the photoinitiator is one or more of 2-ketoglutaric acid and 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone; the catalyst is tetramethylethylenediamine; the solidification temperature and transmittance regulator is one or more of inorganic salt and organic alcohol, the inorganic salt is one or more of sodium chloride, calcium chloride, lithium chloride, potassium chloride and magnesium chloride, and the organic alcohol is one or two of ethylene glycol and glycerol.
3. A method for preparing the acrylamide gel type ice and snow material according to one of claims 1-2, comprising the following steps:
(1) dissolving the acrylamide polymerization monomer, the cross-linking agent, the initiator, the catalyst, the solidification temperature and transmittance regulator in water according to a mass ratio, fully stirring until the acrylamide polymerization monomer, the cross-linking agent, the initiator, the catalyst, the solidification temperature and the transmittance regulator are completely dissolved, and performing vacuum defoaming treatment to obtain a gel-type ice and snow precursor solution;
(2) and (2) injecting the precursor solution in the step (1) into a container or a mold, covering a glass sheet subjected to surface hydrophobic treatment on the container or the mold, and heating or irradiating by ultraviolet light to completely cure the glass sheet to obtain the acrylamide gel type ice snow.
4. The production method according to claim 3, characterized in that: the water in the step (1) is one or two of deionized water, tap water, rainwater and snow water.
5. The production method according to claim 3, characterized in that: the heating temperature in the step (2) is 40-70 ℃, and the heating time is 1.0-3.0 h; the ultraviolet light irradiation wavelength is 365nm, and the irradiation time is 0.5-2.0 h.
6. A sodium alginate gel type ice and snow material with adjustable solidification temperature and transmittance is characterized in that the preparation raw materials are as follows: sodium alginate, a solubilizer, a soluble divalent/trivalent metal ion salt, a crosslinking speed regulator, a plasticizer, a gelling agent, a solidification temperature and transmittance regulator and water, wherein the mass ratio of the raw materials is as follows: 1.0: 2.5-6.5: 0.02-0.5: 0.001-0.5: 0-0.2: 0.05-0.3: 2-10.
7. An icy snow material according to claim 6, characterized in that: the solubilizer is one or more of soft sugar, glucose, fructose, maltose, sucrose and lactose; the soluble divalent metal ion salt is selected from one or more of calcium salt, magnesium salt and ferrous salt, the soluble trivalent metal ion salt is selected from one of aluminum salt and ferric salt, and the calcium salt is one or more of calcium sulfate, calcium chloride, calcium bromide, calcium iodide, calcium nitrate, calcium formate and calcium acetate; the crosslinking speed regulator is tetrasodium pyrophosphate; the plasticizer is one or more of corn starch, tapioca starch, wheat flour and diatomite; the gelling agent is one or more of xanthan gum, pectin and carrageenan; the solidification temperature and transmittance regulator is one or more of inorganic salt and organic alcohol, and the inorganic salt is one or more of sodium chloride, calcium chloride, lithium chloride, potassium chloride and magnesium chloride; the organic alcohol is one or two of ethylene glycol and glycerol.
8. A method for preparing the sodium alginate gel-type ice and snow material according to any one of claims 6 to 7, comprising the following steps:
(1) fully mixing the sodium alginate, the solubilizer, the soluble divalent/trivalent metal ion salt, the crosslinking speed regulator, the plasticizer and the gelling agent;
(2) dissolving a solidification temperature and transmittance regulator in water to obtain a solidification temperature regulating solution;
(3) dissolving the mixed powder particles obtained in the step (1) in the solidification temperature adjusting solution obtained in the step (2), fully stirring until the mixed powder particles are completely dissolved, and then carrying out vacuum degassing treatment to obtain a gel-type ice and snow precursor solution;
(4) and (4) injecting the precursor solution obtained in the step (3) into a container or a mold, covering a glass sheet subjected to surface hydrophobic treatment on the container or the mold, and curing to obtain the sodium alginate gel type ice and snow material with adjustable solidification temperature and transmittance.
9. The method of claim 17, wherein: the water in the step (2) is selected from one or two of deionized water, tap water, rainwater and snow water.
10. The method of claim 17, wherein: and (4) curing for 5-30 min.
CN202010041124.XA 2020-01-15 2020-01-15 Gel type ice and snow material with adjustable solidification temperature and transmittance and preparation method thereof Pending CN111154033A (en)

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CN111704893A (en) * 2020-05-26 2020-09-25 北京理工大学 Magnetic gel ice and snow material and preparation method thereof
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CN112254017A (en) * 2020-10-16 2021-01-22 黑龙江建筑职业技术学院 Manufacturing method of ice masonry for realizing gradual change effect of ice and snow landscape light
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Application publication date: 20200515