阅读说明：本技术 一种蒙脱土逐层矿化沉积形成固化膜的方法 (Method for forming cured film by layer-by-layer mineralization and deposition of montmorillonite ) 是由 刘振东 李公让 张敬辉 周守菊 明玉广 李卉 陈建 张守文 于 2018-08-24 设计创作，主要内容包括：本发明提供一种蒙脱土逐层矿化沉积形成固化膜的方法。其步骤为：首先,室温下,将固体薄片分别交替浸入阳离子聚合物溶液和阴离子聚合物溶液中,浸渍吸附,间隔中用去离子水清洗片状固体上未发生吸附的多余聚合物溶液,并用氮气吹干；然后,在蒙脱土悬浊液中添加阴离子聚合物溶液,再依次将固体薄片浸入阳离子聚合物溶液和添加了阴离子聚合物溶液的蒙脱土悬浊液中,每种溶液中浸渍吸附,间隔中用去离子水清洗固体薄片上未发生吸附的多余溶液,并用氮气吹干。本发明优势在于：固化膜表面比较平整、有一定的机械性能；可对固体表面存在的孔隙及微裂缝进行有效填充,提高固体强度,可广泛应用到钻井井壁加固。(The invention provides a method for forming a curing film by layer-by-layer mineralization and deposition of montmorillonite. The method comprises the following steps: firstly, at room temperature, respectively and alternately immersing solid slices into a cationic polymer solution and an anionic polymer solution, immersing and adsorbing, cleaning excessive polymer solution which is not adsorbed on the slice-shaped solid with deionized water at intervals, and drying with nitrogen; then, adding an anionic polymer solution into the montmorillonite suspension, sequentially immersing the solid sheet into the cationic polymer solution and the montmorillonite suspension added with the anionic polymer solution, soaking and adsorbing each solution, cleaning the excessive solution which is not adsorbed on the solid sheet by deionized water at intervals, and drying by nitrogen. The invention has the advantages that: the surface of the cured film is relatively flat and has certain mechanical property; the composite material can effectively fill pores and microcracks existing on the surface of a solid, improves the strength of the solid, and can be widely applied to reinforcing the well wall of a drilling well.)

1. A method for forming a cured film by layer-by-layer mineralization and deposition of montmorillonite is characterized by comprising the following steps:

firstly, alternately immersing solid slices into a cationic polymer solution and an anionic polymer solution at room temperature for 5-10 min, washing excessive polymer solution which is not adsorbed on the slice-shaped solid with deionized water at intervals of alternate immersion, drying with nitrogen, and alternately immersing for 5-10 cycles;

then, adding the anionic polymer solution into the montmorillonite suspension;

and sequentially immersing the solid sheet into a cationic polymer solution and a montmorillonite turbid liquid added with an anionic polymer solution, immersing and adsorbing each solution for 5-10 min, alternately immersing, cleaning excessive solution which is not adsorbed on the solid sheet by deionized water at intervals, blowing by nitrogen, and alternately immersing for 20-60 cycles.

2. The method for forming the cured film by the layer-by-layer mineralization deposition of montmorillonite as claimed in claim 1, wherein: the cationic polymer comprises one or a combination of more of diethylene glycol diacrylate phthalate, polyetherimide and phenylpropanolamine hydrochloride; the anionic polymer comprises one or more of polyacrylic acid and sodium polystyrene sulfonate.

3. The method for the layer-by-layer mineralization deposition of montmorillonite to form a cured film according to claim 1 or 2, wherein: the mass percentage of the cationic polymer solution is 0.1-0.2%, and the pH value is 4.0-4.5; the mass percentage of the anionic polymer solution is 0.1-0.2%, and the pH value is 8.0-8.5; the mass percentage of the montmorillonite suspension is 0.1-0.2%, and the pH value is 8.0-8.5.

4. The method for forming the cured film by the layer-by-layer mineralization deposition of montmorillonite as claimed in claim 3, wherein: the solid sheet comprises one of a silicon wafer, a rock sheet, a glass sheet and a filter paper sheet.

Technical Field

The invention relates to a method for forming a cured film by layer-by-layer mineralization and deposition of montmorillonite, belonging to the technical field of biomimetic synthesis of biomineralization materials.

Background

Layer-by-layer assembly is a deposition technique for multilayer films. In 1966, Iler first used oppositely charged colloidal particles to alternately assemble and prepare multilayer films. Furthermore, he also points out that this technique can be used not only for the assembly of colloidal particles, but also extended to the field of the assembly of multivalent ions, surfactants, water-soluble polymers and even proteins. This technique has not received wide attention at that time. Subsequently, Decher re-uses this technique and has a better interpretation, and layer-by-layer assembly techniques have therefore begun to be greatly developed. Specifically, a substrate with positive charges on the surface is firstly immersed into a polymer solution with negative charges, and then deionized water is used for eluting physically adsorbed polymers; the resulting substrate was immersed in a positively charged polymer solution, and then washed with deionized water as well. By repeating these two steps, a self-assembled multilayer film can be obtained.

Inorganic nanosheet materials with unique material properties can also be combined with layer-by-layer assembly technology, and Ferguson and the like report that a multilayer film is assembled by utilizing a positive polyelectrolyte and silicate nanosheets. The multilayer film with the thickness of 200nm has regular structure and obvious X-ray diffraction signal. Poddiadlo et al prepared ultra-strong polymer nanocomposite membrane materials using polyvinyl alcohol (PVA) and montmorillonite (MTM). The nanosheets are closely packed and have a well-defined planar orientation. Through mechanical property tests, the authors show that the final tensile strength and Young's modulus of the pure PVA/MTM composite membrane are respectively 4 times and 10 times of those of the pure PVA polymer membrane, and after glutaraldehyde crosslinking, various mechanical property parameters of the multilayer membrane are greatly improved. Different from mechanical properties, Hammond and its collaborators research the ion transmission property of the multilayer film after adding the inorganic nanosheet material. The authors assembled films using PEI, hectorite and polyethylene oxide (PEO) through hydrogen bonding and electrostatic interactions. The test results show that under the condition of 0% relative humidity, the anisotropic structure with the layers has the ion transmission speed in each layer of the film which is 100 times higher than that between the layers.

If the biomimetic mineralized material is prepared by using a layer-by-layer assembly technology, the biomimetic mineralized material can be used for multiple aspects of petroleum drilling and has wide application, such as drilling well wall reinforcement and the like. Existing researchers have proposed methods to control the crystalline structure, shape and assembly during the growth of calcium carbonate crystals. For example, under the action of gel, a spherulite calcium carbonate polycrystalline complex with a porous hexagonal morphology (J.H. Zhan, H.P. Lin, C.Y Mou, adv. Mater. 2003, 15, 621, 623.); the DHBC-surfactant compound micelle is used as a template to synthesize the calcite hollow sphere calcium carbonate compound (L.Qi, J.Li, J.Ma, adv. Mater. 2002, 14, 300-303.) with the micron size. The patent with application number 200710042997.7 provides a nano-layered calcium carbonate bionic composite material, which is a multi-layer structure formed by the steps that low-molecular-weight organic matters participate in the reaction process of calcium chloride and sodium carbonate, and are guided to calcite to form a nano-thin-layer structure, so that the nano-thin layer is directionally assembled by the layer structure. These studies play an important role in promoting the biomimetic synthesis of biomineralization materials, but the biomineralization materials with natural calcium carbonate structures cannot be grown, or the method and the material properties are still to be further improved.

Disclosure of Invention

The invention aims to provide a method for forming a curing film by layer-by-layer mineralization and deposition of montmorillonite, which is used for forming the curing film by layer-by-layer deposition and mineralization of montmorillonite particles on the surface of a solid aiming at the defects in the prior art. The cured film is smooth and flat, has certain mechanical property, and can be used for improving the strength of the solid surface.

In order to achieve the purpose of the invention, the technical scheme of the invention is realized as follows:

a method for forming a cured film by layer-by-layer mineralization and deposition of montmorillonite comprises the following steps:

firstly, alternately immersing solid slices into a cationic polymer solution and an anionic polymer solution at room temperature for 5-10 min, washing excessive polymer solution which is not adsorbed on the slice-shaped solid with deionized water at intervals of alternate immersion, drying with nitrogen, and alternately immersing for 5-10 cycles;

and then adding an anionic polymer solution into the montmorillonite turbid liquid, sequentially immersing the solid sheet into the cationic polymer solution and the montmorillonite turbid liquid added with the anionic polymer solution, immersing and adsorbing each solution for 5-10 min, alternately immersing, cleaning the residual solution which is not adsorbed on the solid sheet by deionized water at intervals, blowing the residual solution by nitrogen, and alternately immersing for 20-60 cycles.

In the above scheme, the cationic polymer comprises one or a combination of more of diethylene glycol diacrylate Phthalate (PDDA), Polyetherimide (PEI), and phenylpropanolamine hydrochloride (PPA); the anionic polymer comprises one or more of polyacrylic acid (PAA) and sodium polystyrene sulfonate (PSS).

In the scheme, the mass percent of the cationic polymer solution is 0.1-0.2%, and the pH value is 4.0-4.5; the mass percentage of the anionic polymer solution is 0.1-0.2%, and the pH value is 8.0-8.5; the mass percentage of the montmorillonite suspension is 0.1-0.2%, and the pH value is 8.0-8.5.

In the technical scheme, the solid sheet comprises one of a silicon wafer, a rock sheet, a glass sheet and a filter paper sheet.

Compared with the prior art, the invention has the advantages that:

(1) the surface of the curing film is relatively flat and has certain mechanical property;

(2) the invention can effectively fill the pores and microcracks on the solid surface, improve the solid strength and can be widely applied to the reinforcement of the well wall of the well.

Drawings

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Detailed Description