CN112058214B - Method for preparing montmorillonite film capable of stably existing in solution - Google Patents
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000000137 annealing Methods 0.000 claims abstract description 15
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 12
- 229910000271 hectorite Inorganic materials 0.000 claims description 12
- 239000008151 electrolyte solution Substances 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910021647 smectite Inorganic materials 0.000 claims 4
- 206010040844 Skin exfoliation Diseases 0.000 claims 1
- 238000004299 exfoliation Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000003607 modifier Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/40—Clays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
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Abstract
The invention discloses a method for preparing a montmorillonite film capable of stably existing in a solution, which comprises the following steps: 1) Dispersing a certain amount of montmorillonite in a solvent, and preparing a montmorillonite film A1 by vacuum filtration; 2) The montmorillonite film A1 obtained in the step 1) is put in a temperature range of 20-70 DEG o Drying for 10-20h under the condition of C, 90-120 o Low temperature annealing treatment for 5-10h under the condition of C, 200-500 g o C, annealing at low temperature for 20-30h to obtain the montmorillonite film A2 which can stably exist in the solution. According to the invention, the montmorillonite film capable of stably existing in the solution is prepared through vacuum filtration, simple low-temperature heat treatment and annealing treatment, no organic modifier is required to be introduced, the operation is simple, the influence of the low-temperature annealing process on the ordered layer structure in the film is small, the obtained annealed montmorillonite film can stably exist in the solution for more than 28 days, and the long-term stable application of the montmorillonite film is facilitated.
Description
Technical Field
The invention belongs to the field of montmorillonite processing, and particularly relates to a preparation method of a montmorillonite film capable of stably existing in a solution.
Background
Montmorillonite is a typical 2. The montmorillonite is low in price, environment-friendly, high in chemical stability and thermal stability and has a natural layered structure and excellent adsorption performance, and the montmorillonite is widely used for researching and preparing novel efficient gel adsorbents, mineral-based heat storage materials and other advanced mineral functional materials.
Because the surface of the montmorillonite is naturally negatively charged and has stronger hydrophilicity, the montmorillonite is easy to generate hydration expansion and stripping in water, the separated montmorillonite sheet layers with the nanometer-scale thickness stably dispersed in the solution can be used for preparing the montmorillonite film with the ordered layered structure through simple suction filtration and recombination, and the internal layer structure of the montmorillonite film prepared by the method can be used as a fluid transmission channel so as to have application potential of realizing ion selection, energy conversion and the like. However, due to the natural hydration and expansion characteristics of clay minerals, the montmorillonite film material prepared by direct suction filtration has extremely poor stability in water, and the film form cannot be maintained, so that the clay usually needs to be subjected to surface modification in a reassembling process, for example, a film is prepared by reassembling montmorillonite nanosheets after CTAB modification reported in related researches (J. Mater. Chem.A., 2019,7, 14089). The introduction of the organic modifier not only makes the process of reassembling complex, but also has certain influence on the structure of the nano fluid channel in the two-dimensional direction, and the organic matter has poor high temperature resistance, thereby limiting the application range of preparing the clay mineral film material.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing a montmorillonite film which can stably exist in a solution aiming at the defects of the prior art. The method can obviously improve the stability of the hydrophilic montmorillonite film in the solution only through a simple low-temperature heat treatment process, does not need modification treatment, and has simple and convenient operation process.
The technical scheme adopted by the invention for solving the problems is as follows:
a method for preparing montmorillonite film capable of stably existing in solution comprises the following steps:
1) Dispersing a certain amount of montmorillonite sample, and preparing a montmorillonite film A1 by vacuum suction filtration;
2) Drying the montmorillonite film A1 obtained in the step 1) at the temperature of 20-70 ℃ for 10-20h, carrying out low-temperature annealing treatment at the temperature of 90-120 ℃ for 5-10h, and carrying out low-temperature annealing treatment at the temperature of 200-500 ℃ for 20-30h to obtain a montmorillonite film sample A2 capable of stably existing in the solution.
In the above scheme, the montmorillonite sample in step 1) is one or more of hectorite, sodium montmorillonite, calcium montmorillonite or any other metal montmorillonite.
In the above scheme, the montmorillonite sample in step 1) is an untreated montmorillonite sample or a montmorillonite sample subjected to liquid/gas phase stripping treatment or any other desired pretreatment, and the like.
In the scheme, the solvent in the step 1) is pure water or electrolyte solution and the like, and the dispersion concentration of the montmorillonite in the solvent is 1-10 wt%. Wherein the electrolyte solution comprises various kinds of electrolyte such as LiCl, naCl, KCl, mgCl 2 And various metal ion salt solutions, etc., and the concentration range is generally 0.01 to 1mol/L.
In the above embodiment, the solution in which the montmorillonite film A2 can exist stably includes pure water; liCl, naCl, KCl, mgCl 2 Various metal ion salt solutions (concentration range 0.01-1 mol/L), etc.; and one or more of organic solvents such as ethanol and isopropanol or their aqueous solutions. Wherein the organic solvent is an organic solvent which is mutually soluble with water; the concentration of the aqueous solution of the organic solvent may be generally in the range of 10 to 100%.
In the scheme, the montmorillonite film which can stably exist in the solution is prepared by the method.
In the above aspect, the montmorillonite film is stably present in water, an electrolyte solution or an organic solvent solution for 28 days or more.
Compared with the prior art, the invention has the beneficial effects that: in the low-temperature annealing process of the montmorillonite, cations such as lithium ions among montmorillonite layers can enter octahedral vacancies of montmorillonite layers, so that part of negative charges on the surface of the montmorillonite caused by Al substituted by low-valence cations are neutralized, the spacing between the montmorillonite layers is reduced after the low-temperature annealing, the part of the negative charges is neutralized, and the dispersibility and the hydration expansibility of the montmorillonite are obviously reduced. Then, the montmorillonite film prepared by reassembling can be greatly improved in stability after low-temperature annealing treatment and stably exists in an aqueous solution for a long time. The low-temperature annealing treatment process does not need to introduce an organic modifier, is simple and efficient in operation process, and ensures long-term stable application of the hydrophilic montmorillonite film in the processes of ion selection, energy conversion and the like.
Drawings
FIG. 1 is a graph showing a change within 1 hour of the montmorillonite film A1 of example 2 being directly placed in deionized water after drying at room temperature.
FIG. 2 shows the modified case of the montmorillonite film A2 of example 2 in deionized water at 1d, 3d, 7d, 28 d.
In FIG. 3, (a) is a surface contact angle test of the montmorillonite film A2 in example 2; (b) XRD test results of the dried montmorillonite film A1, the montmorillonite film A2, and the rehydrated montmorillonite film A2 in example 2.
Detailed Description
For a better understanding of the present invention, the following examples are given to further illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
A method for preparing a montmorillonite film capable of stably existing in a solution comprises the following specific steps:
1) Dispersing 1.5g of hectorite sample in pure water to prepare 30mL of 5wt% hectorite pulp, preparing a montmorillonite film A1 by vacuum filtration, and separating the montmorillonite film A1 from a filter membrane;
2) The montmorillonite film A1 is dried for 15h under the condition of 60 ℃, then annealed for 6h under the condition of 100 ℃, and then annealed for 24h under the condition of 250 ℃ to obtain a montmorillonite film sample A2 which can stably exist in water for more than 28 d.
Example 2
A method for preparing montmorillonite film capable of stably existing in solution comprises the following steps:
1) A1.5 g sample of hectorite was dispersed in pure water to make 30mL of a 5wt% hectorite pulp with a strength of 267W/cm 2 Carrying out ultrasonic stripping for 10min under the condition, preparing a montmorillonite film A1 by vacuum filtration, and separating the montmorillonite film A1 from a filter membrane;
2) The montmorillonite film A1 is dried for 15h at 60 ℃, then annealed at 100 ℃ for 6h, and then annealed at 230 ℃ for 24h to obtain a montmorillonite film sample A2 which can stably exist in water for more than 28 d.
As shown in fig. 1, the montmorillonite film A1 has poor stability in water, and can be completely disintegrated only by soaking for 1 hour; after two stages of low-temperature annealing treatment, the stability of the montmorillonite film A2 is greatly improved, and the montmorillonite film A can stably exist in water for more than 28d (figure 2).
As shown in fig. 3, the surface of the montmorillonite film A2 still exhibited hydrophilicity, and the contact angle was about 69.5 ° (fig. a). XRD test results of the montmorillonite film show that the interlayer d value of the montmorillonite film A1 which is directly suction-filtered and reassembled is 1.251nm, the interlayer spacing is shrunk by the low-temperature annealing treatment process, the interlayer d value of the montmorillonite film A2 is reduced to about 0.9187nm, and the interlayer d value is increased to 0.9725nm after the montmorillonite film is soaked in water again and hydrated. The montmorillonite film A2 after low-temperature annealing treatment has a sub-nanometer scale capillary structure, and can be used for preparing various advanced micro-nano flow components.
Example 3
A method for preparing a montmorillonite film capable of stably existing in a solution comprises the following specific steps:
1) A3 g sodium-based montmorillonite sample was dispersed in pure water to make 30mL of 10wt% sodium-based montmorillonite pulp with a strength of 267W/cm 2 Carrying out ultrasonic stripping for 10min under the condition, preparing a montmorillonite film A1 by vacuum filtration, and separating the montmorillonite film A1 from a filter membrane;
2) The montmorillonite film A1 is dried for 15h at 60 ℃, then annealed at 100 ℃ for 6h, and then annealed at 230 ℃ for 24h to obtain a montmorillonite film sample A2 which can stably exist in KCl salt solution (1M) for more than 28 d.
Example 4
A method for preparing a montmorillonite film capable of stably existing in a solution comprises the following specific steps:
1) A0.3 g sample of hectorite was dispersed in LiCl solution (0.5M) to make 30mL of a 1wt% hectorite pulp with a strength of 267W/cm 2 Carrying out ultrasonic stripping for 10min under the condition, preparing a montmorillonite film A1 by vacuum filtration, and separating the montmorillonite film A1 from a filter membrane;
2) The montmorillonite film A1 is dried for 15h at 60 ℃, then annealed at 100 ℃ for 6h, and then annealed at 300 ℃ for 24h to obtain a montmorillonite film sample A2 which can stably exist in ethanol solution (95%) for more than 28 days.
Example 5
A method for preparing a montmorillonite film capable of stably existing in a solution comprises the following specific steps:
1) A1.5 g sample of hectorite was dispersed in pure water to make 30mL of a 5wt% hectorite pulp with a strength of 267W/cm 2 Carrying out ultrasonic stripping for 10min under the condition, preparing a montmorillonite film A1 by vacuum filtration, and separating the montmorillonite film A1 from a filter membrane;
2) The montmorillonite film A1 is dried for 15h at 60 ℃, then annealed at 100 ℃ for 6h, and then annealed at 500 ℃ for 24h to obtain a montmorillonite film sample A2 which can stably exist in water for more than 28 d.
Comparative example 1
A method for preparing a montmorillonite film comprises the following specific steps:
1) A1.5 g sample of hectorite was dispersed in pure water to make 30mL of a 5wt% hectorite pulp with a strength of 267W/cm 2 Carrying out ultrasonic stripping for 10min under the condition, preparing a montmorillonite film A1 by vacuum filtration, and separating the montmorillonite film A1 from a filter membrane;
2) The montmorillonite film A1 was dried at 60 ℃ for 15 hours, and then annealed at 100 ℃ for 6 hours to obtain a montmorillonite film sample A3 which could not exist stably in water and completely disintegrated only within 1-3 hours.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.
Claims (5)
1. A method for preparing a montmorillonite film capable of stably existing in a solution is characterized by comprising the following specific steps:
1) Dispersing montmorillonite in a solvent, and preparing a montmorillonite film A1 by vacuum filtration;
2) Drying the montmorillonite film A1 obtained in the step 1) at the temperature of 20-70 ℃ for 10-20h, annealing at the low temperature of 90-120 ℃ for 5-10h, and annealing at the low temperature of 200-500 ℃ for 20-30h to obtain a montmorillonite film A2 which can stably exist in a solution;
in the step 1), the solvent is pure water or electrolyte solution, and the dispersion concentration of montmorillonite in the solvent is 1-10 wt%; the concentration range of the electrolyte solution is 0.01-1 mol/L;
the stable existing solution of the montmorillonite film A2 is one or more of pure water, electrolyte solution and organic solution.
2. The method according to claim 1, wherein the montmorillonite in step 1) is one or a mixture of more of hectorite, sodium montmorillonite, calcium montmorillonite or any other metal-based montmorillonite.
3. The method according to claim 1, wherein the smectite in step 1) is a smectite sample that is untreated or has been subjected to a liquid/gas phase exfoliation treatment or any other desired pretreatment.
4. A montmorillonite film which can be stably present in a solution prepared by the method of claim 1.
5. The smectite film according to claim 4, wherein the smectite film is stable in water or an electrolyte solution or an organic solution for a period of 28 days or more.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724358A (en) * | 2004-07-22 | 2006-01-25 | 中国地质大学（北京） | Key tech. for preparing titanium dioxide post-ylene-montmorilloid by titanium tetrachloride hydrolysis process |
| CN101898114A (en) * | 2010-08-19 | 2010-12-01 | 西安科技大学 | Method for preparing montmorillonite forming adsorbent |
| CN102744056A (en) * | 2012-06-30 | 2012-10-24 | 浙江工业大学 | Ti-V loaded aluminum-pillared montmorillonite heterogeneous catalyst and application thereof |
| CN103044909A (en) * | 2012-11-25 | 2013-04-17 | 安徽六方重联机械股份有限公司 | Packaging plastic substrate thin film containing nylon PA6 |
| CN106145442A (en) * | 2016-07-31 | 2016-11-23 | 武汉理工大学 | A kind of method preventing montmorillonite from peeling off in aqueous |
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- 2020-09-01 CN CN202010904034.9A patent/CN112058214B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724358A (en) * | 2004-07-22 | 2006-01-25 | 中国地质大学（北京） | Key tech. for preparing titanium dioxide post-ylene-montmorilloid by titanium tetrachloride hydrolysis process |
| CN101898114A (en) * | 2010-08-19 | 2010-12-01 | 西安科技大学 | Method for preparing montmorillonite forming adsorbent |
| CN102744056A (en) * | 2012-06-30 | 2012-10-24 | 浙江工业大学 | Ti-V loaded aluminum-pillared montmorillonite heterogeneous catalyst and application thereof |
| CN103044909A (en) * | 2012-11-25 | 2013-04-17 | 安徽六方重联机械股份有限公司 | Packaging plastic substrate thin film containing nylon PA6 |
| CN106145442A (en) * | 2016-07-31 | 2016-11-23 | 武汉理工大学 | A kind of method preventing montmorillonite from peeling off in aqueous |
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