WO2019033486A1 - 环境友好型酸洗缓蚀剂与其应用 - Google Patents

环境友好型酸洗缓蚀剂与其应用 Download PDF

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WO2019033486A1
WO2019033486A1 PCT/CN2017/101734 CN2017101734W WO2019033486A1 WO 2019033486 A1 WO2019033486 A1 WO 2019033486A1 CN 2017101734 W CN2017101734 W CN 2017101734W WO 2019033486 A1 WO2019033486 A1 WO 2019033486A1
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pickling
carbon quantum
polyaromatic
containing carbon
environmentally
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PCT/CN2017/101734
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English (en)
French (fr)
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王立平
崔明君
任思明
覃松绿
赵海超
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中国科学院宁波材料技术与工程研究所
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Publication of WO2019033486A1 publication Critical patent/WO2019033486A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/068—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors compounds containing a C=C bond
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel

Definitions

  • the invention relates to a corrosion inhibitor, in particular to an environmentally friendly polyaromatic nitrogen-containing carbon quantum dot pickling corrosion inhibitor for carbon steel pickling, a preparation method and application thereof, and belongs to the technical field of metal anticorrosion.
  • Pickling is an inexpensive, simple and effective method to remove dirt and rust on the surface of metal materials.
  • the most commonly used acids are mainly hydrochloric acid and sulfuric acid, and hydrochloric acid is the most widely used pickling agent; however, in the cleaning process, hydrochloric acid is highly corrosive to metallic materials, causing over-etching;
  • hydrogen generated by the reaction of hydrochloric acid with metal causes hydrogen embrittlement corrosion of the metal material, and the generation of hydrogen gas brings out a large amount of acid mist, which deteriorates working conditions. Therefore, it is necessary to add a corrosion inhibitor during the pickling process to reduce corrosion of the metal material and volatilization of the acid mist.
  • corrosion inhibitors mainly include inorganic corrosion inhibitors and organic corrosion inhibitors.
  • Traditional inorganic corrosion inhibitors mainly include nitrites and chromates, but such corrosion inhibitors can cause great harm to humans, animals and the ecological environment; while organic corrosion inhibitors such as phosphorus and sulfur have good properties. The slow release effect, but it also has great harm to the environment. Therefore, with the improvement of human environmental awareness and the idea of sustainable development, the development of non-toxic and efficient environmentally friendly corrosion inhibitors has become a new direction for the study of corrosion inhibitors.
  • the main object of the present application is to provide an environmentally friendly pickling corrosion inhibitor and its use to overcome the deficiencies of the prior art.
  • the technical solution adopted by the present application includes:
  • the embodiments of the present application provide the use of polyaromatic nitrogen-containing carbon quantum dots for preparing a pickling inhibitor.
  • the polyaromatic ring nitrogen-containing carbon quantum dots have a particle diameter of 3 to 4 nm.
  • the constituent elements of the polyaromatic nitrogen-containing carbon quantum dots include C, N and O.
  • the preparation method of the polyaromatic ring nitrogen-containing carbon quantum dots comprises:
  • reaction monomer and the solvent are uniformly mixed, and then heated to carry out a solvothermal reaction to cause dehydration, decarboxylation, and bonding between the molecules to obtain a polyaromatic nitrogen-containing carbon quantum dot.
  • the reactive monomer comprises a compound containing a benzene ring and an amino group.
  • the reactive monomer includes an aminobenzoic acid compound and/or a phenylenediamine compound.
  • the reactive monomer includes any one or a combination of two or more of 4-aminosalicylic acid, 5-aminosalicylic acid, o-phenylenediamine, p-phenylenediamine, and m-phenylenediamine.
  • the solvothermal reaction has a temperature of from 180 to 200 ° C for a period of from 12 to 18 hours.
  • volume-to-mass ratio of the solvent to the reaction monomer is 5 mL: 0.1 g to 20 mL: 0.1 g, preferably 5 mL: 0.1 g to 10 mL: 0.1 g.
  • the embodiment of the present application also provides an environmentally friendly pickling inhibitor, the corrosion inhibitor comprising a polyaromatic nitrogen-containing carbon quantum dot.
  • the polyaromatic ring nitrogen-containing carbon quantum dots have a particle diameter of 3 to 4 nm.
  • the constituent elements of the polyaromatic nitrogen-containing carbon quantum dots include C, N and O.
  • the embodiments of the present application also provide the aforementioned environmentally friendly pickling inhibitor in the field of metal corrosion protection.
  • the application comprises: adding the environmentally friendly pickling inhibitor to the pickling agent before pickling the metal material, wherein the environmentally friendly pickling inhibitor is added at a concentration of 0 to 200 mg ⁇ L -1 .
  • the embodiment of the present application further provides a pickling method for a metal material, which comprises: washing the metal material with an acid pickling agent containing the environmentally friendly pickling inhibitor described above.
  • the environmentally friendly pickling inhibitor provided by the present application includes polyaromatic nitrogen-containing carbon quantum dots.
  • the polyaromatic ring nitrogen-containing carbon quantum dots are mainly prepared by a solvothermal method using aminobenzoic acid, phenylenediamine or the like as a main raw material, and have the characteristics of simple synthesis, no toxicity, no toxicity, and easy to be dissolved in acid;
  • the pickling corrosion inhibitor containing the polycyclic ring nitrogen-containing carbon quantum dots is simple to use, and the hydrochloric acid solution can be used as the cleaning liquid to pickle the carbon steel, which can effectively inhibit the corrosion of the carbon steel in the acid solution.
  • Carbon steel has a high sustained release rate, low dosage, environmental protection and high efficiency.
  • 1a and 1b are respectively the content of polyaromatic nitrogen-containing carbon in the environmentally friendly pickling inhibitor obtained in Example 1 of the present application.
  • 1c, 1d, and 1e respectively correspond to a two-dimensional profile of the polyaromatic nitrogen-containing carbon quantum dots passing through the three curves in FIG. 1b;
  • 1f is an XPS spectrum diagram of 4-aminosalicylic acid and the prepared polyaromatic nitrogen-containing carbon quantum dots in Example 1 of the present application;
  • Example 2 is a polarization diagram of a 1 mol ⁇ L -1 HCl solution containing different concentrations of environmentally friendly pickling inhibitors after being immersed in carbon steel for 0.5 h in Example 1 of the present application;
  • Example 3 is a graph showing the inhibition efficiency with the immersion time under the optimum corrosion inhibitor concentration (10 mg L -1 ) in Example 1 of the present application;
  • 4a is a scanning electron micrograph of the Q235 carbon steel in the hydrochloric acid solution having a corrosion inhibitor concentration of 1 mol ⁇ L -1 for 72 hours in Example 1 of the present application;
  • 4b is a scanning electron micrograph of the Q235 carbon steel in the first embodiment of the present application after being immersed in a hydrochloric acid solution having a corrosion inhibitor concentration of 10 mg L -1 for 72 hours;
  • Example 5 is a polarization diagram of a 1 mol ⁇ L -1 HCl solution containing different concentrations of environmentally friendly pickling inhibitors after being immersed in carbon steel for 0.5 h in Example 2 of the present application;
  • Example 6 is a graph showing the inhibition efficiency with the immersion time under the optimum corrosion inhibitor concentration (200 mg L -1 ) in Example 2 of the present application;
  • Example 7 is a scanning electron micrograph of the Q235 carbon steel in the hydrochloric acid solution having a corrosion inhibitor concentration of 200 mg L -1 for 72 hours in Example 2 of the present application;
  • Example 8 is a polarization diagram of a carbon steel immersed in a carbon steel for 72 hours in Example 3 of the present application with a 1 mol ⁇ L -1 HCl solution containing different concentrations of environmentally friendly pickling inhibitors;
  • Example 9 is a graph showing the inhibition efficiency with the immersion time under the optimum corrosion inhibitor concentration (200 mg L -1 ) in Example 3 of the present application.
  • Figure 10 is a scanning electron micrograph of the Q235 carbon steel in Example 3 of the present application after being immersed in a hydrochloric acid solution having a corrosion inhibitor concentration of 200 mg L -1 for 72 hours.
  • carbon quantum dots have caused extensive research in the field of nanomaterials. Their fluorescence, water solubility and low toxicity make these carbon quantum dots have high application value in the field of biosensing. Industry R&D personnel have reported the successful preparation of fluorescent, low-toxic nitrogen-containing carbon quantum dots by heat treatment of 4-aminosalicylic acid solvent. It is also reported that phenylenediamine solvent also exhibits good fluorescence after heat treatment. Cell compatibility. By comparison, we can find that both carbon quantum dots have benzene ring and nitrogen atom; and the sustained release agent with this structure usually has a certain physical and chemical action with the metal surface to reduce the corrosion of the metal.
  • the inventors of the present invention have been able to propose the technical solution of the present application through long-term research and extensive practice, mainly by using a benzoic acid and phenylenediamine as main raw materials to obtain a polyaromatic ring by a solvothermal method.
  • Environmentally friendly pickling inhibitor for nitrogen-containing carbon quantum dots The technical solution, its implementation process and principle, etc. will be further explained as follows.
  • One aspect of an embodiment of the present application provides a polyaromatic ring nitrogen-containing carbon quantum dot for use in preparing a pickling inhibitor.
  • the polyaromatic ring nitrogen-containing carbon quantum dots have a particle diameter of 3 to 4 nm.
  • the constituent elements of the polyaromatic nitrogen-containing carbon quantum dots include C, N and O.
  • the preparation method of the polyaromatic ring nitrogen-containing carbon quantum dots comprises:
  • reaction monomer and the solvent are uniformly mixed, and then heated to carry out a solvothermal reaction, and dehydration, decarboxylation and bonding between the molecules occur, and finally a polyaromatic nitrogen-containing carbon quantum dot is obtained.
  • the reactive monomer comprises a compound containing a benzene ring and an amino group.
  • the reactive monomer comprises an aminobenzoic acid compound and/or a phenylenediamine compound.
  • the reactive monomer is selected from any one or a combination of two or more of 4-aminosalicylic acid, 5-aminosalicylic acid, o-phenylenediamine, p-phenylenediamine, and m-phenylenediamine. , but not limited to this.
  • the solvothermal reaction has a temperature of from 180 to 200 ° C for a period of from 12 to 18 hours.
  • volume-to-mass ratio of the solvent to the reactive monomer (which may also be referred to as a liquid-solid ratio) ranges from 5 mL: 0.1 g to 20 mL: 0.1 g, preferably a volume-to-mass ratio of 5 mL: 0.1 g to 10 mL: 0.1 g.
  • the solvent is selected from the group consisting of ethanol.
  • the method for preparing the polyaromatic ring nitrogen-containing carbon quantum dot further comprises: after the reaction is completed, the reaction system is purified by placing in a dialysis bag having a molecular weight cut off of 1.0 kDa to 5.0 kDa, and then removing the solvent and drying to obtain a solution. More Aromatic ring nitrogen-containing carbon quantum dots.
  • the dialysis bag has a molecular weight cut off of 1.0 kDa to 3.0 kDa.
  • the preparation method of the polyaromatic ring nitrogen-containing carbon quantum dots may include:
  • the raw material is dissolved in an appropriate amount of absolute ethanol and heated at 200 ° C for 18 hours, and the raw materials include 4-aminosalicylic acid, 5-aminosalicylic acid, o-phenylenediamine, p-phenylenediamine, and m-benzene. Diamines, and other benzene ring/amino containing monomers.
  • reaction solution was placed in a 3.0 kDa dialysis bag for purification to remove unreacted raw materials.
  • the purified product is centrifuged to remove the solvent, and dried under vacuum to obtain the polyaromatic ring nitrogen-containing carbon quantum dots.
  • Another aspect of an embodiment of the present application provides an environmentally friendly pickling inhibitor comprising a polyaromatic nitrogen-containing carbon quantum dot.
  • the polyaromatic ring nitrogen-containing carbon quantum dots have a particle diameter of 3 to 4 nm.
  • the constituent elements of the polyaromatic nitrogen-containing carbon quantum dots include C, N and O.
  • the preparation method of the polyaromatic ring nitrogen-containing carbon quantum dots comprises:
  • reaction monomer is uniformly mixed with the solvent, and then heated to carry out a solvothermal reaction to obtain a polyaromatic ring nitrogen-containing carbon quantum dot.
  • the reactive monomer comprises a compound containing a benzene ring and an amino group.
  • the reactive monomer comprises an aminobenzoic acid compound and/or a phenylenediamine compound.
  • the reactive monomer is selected from any one or a combination of two or more of 4-aminosalicylic acid, 5-aminosalicylic acid, o-phenylenediamine, p-phenylenediamine, and m-phenylenediamine. , but not limited to this.
  • the solvothermal reaction has a temperature of from 180 to 200 ° C for a period of from 12 to 18 hours.
  • volume-to-mass ratio of the solvent to the reactive monomer (which may also be referred to as a liquid-solid ratio) ranges from 5 mL: 0.1 g to 20 mL: 0.1 g, preferably a volume-to-mass ratio of 5 mL: 0.1 g to 10 mL: 0.1 g.
  • the solvent is selected from the group consisting of ethanol.
  • the method for preparing the polyaromatic ring nitrogen-containing carbon quantum dot further comprises: after the reaction is finished, purifying the reaction system in a dialysis bag having a molecular weight cut off of 1.0 to 5.0 kDa, and then removing the solvent and drying to obtain the Polyaromatic ring nitrogen-containing carbon quantum dots, wherein the preferred dialysis bag has a molecular weight cutoff of 1.0 to 3.0 kDa.
  • Another aspect of an embodiment of the present application also provides the use of the aforementioned environmentally friendly pickling inhibitor, particularly Application in the field of metal corrosion protection.
  • the application comprises: adding the environmentally friendly pickling inhibitor to the pickling agent before pickling the metal material, wherein the environmentally friendly pickling inhibitor is added at a concentration of 0 to 200 mg ⁇ L -1 .
  • the pickling agent comprises hydrochloric acid.
  • Another aspect of the embodiments of the present application further provides a pickling method for a metal material, comprising: washing the metal material with an acid pickling agent containing the environmentally friendly pickling inhibitor described above.
  • the metal material includes carbon steel or the like, but is not limited thereto.
  • the principle that the environmentally friendly pickling inhibitor obtained in the present application can carry out metal corrosion protection is that the polyaromatic nitrogen-containing carbon quantum dots prepared by the solvothermal method interact with the surface of the carbon steel to form an adsorption layer on the surface of the carbon steel. , which can slow down the corrosion of metals.
  • the Q235 carbon steel steel sheet was immersed in a 1 mol ⁇ L -1 hydrochloric acid solution, and the environmentally friendly pickling corrosion inhibitor prepared in the present example was added to make the corrosion inhibitor concentration 0 mg ⁇ L -1 , 1 mg ⁇ L respectively. -1 , 5 mg ⁇ L -1 , 10 mg ⁇ L -1 , 50 mg ⁇ L -1 , 100 mg ⁇ L -1 , and immersed at room temperature for 0.5 hour for polarization test.
  • the polarization test results are shown in Figure 2.
  • the corrosion inhibition efficiencies at different inhibitor concentrations were 0, 12.3%, 86.7%, 90.9%, 89.3%, and 87.2%, respectively. It is 10 mg ⁇ L -1 .
  • the Q235 carbon steel steel sheet is immersed in a 1 mol ⁇ L -1 hydrochloric acid solution, and the concentration of the environmentally friendly pickling inhibitor prepared in the present embodiment is the concentration having the maximum corrosion inhibition rate, that is, 10 mg ⁇ L -1 .
  • the corrosion inhibition efficiency as a function of immersion time is shown in Fig. 3.
  • the Q235 carbon steel steel sheet was immersed in a 1 mol ⁇ L -1 hydrochloric acid solution, and the environmentally friendly pickling corrosion inhibitor prepared in the present example was added to make the corrosion inhibitor concentration 0 mg ⁇ L -1 , 10 mg ⁇ L, respectively. -1 , 50 mg ⁇ L -1 , 100 mg ⁇ L -1 , 200 mg ⁇ L -1 , and immersed for 0.5 hour at room temperature for polarization test.
  • the polarization test results are shown in Figure 5.
  • the sustained release efficiencies at different inhibitor concentrations were 0, 71%, 86%, 88%, and 88%, respectively.
  • the Q235 carbon steel steel sheet is immersed in a 1 mol ⁇ L -1 hydrochloric acid solution, and the concentration of the environmentally friendly pickling inhibitor prepared in the present embodiment is the concentration having the maximum corrosion inhibition rate, that is, 200 mg ⁇ L -1 .
  • the corrosion inhibition efficiency as a function of immersion time is shown in Fig. 6.
  • the Q235 carbon steel steel sheet was immersed in a 1 mol ⁇ L -1 hydrochloric acid solution, and the environmentally friendly pickling corrosion inhibitor prepared in the present example was added to make the corrosion inhibitor concentration 0 mg ⁇ L -1 , 10 mg ⁇ L, respectively. -1 , 50 mg ⁇ L -1 , 100 mg ⁇ L -1 , 200 mg ⁇ L -1 , and immersed for 72 hours at room temperature for polarization test.
  • the Q235 carbon steel steel sheet is immersed in a 1 mol ⁇ L -1 hydrochloric acid solution, and the concentration of the environmentally friendly pickling inhibitor prepared in the present embodiment is the concentration having the maximum corrosion inhibition rate, that is, 200 mg ⁇ L -1 .
  • the corrosion inhibition efficiency as a function of immersion time is shown in Fig. 9.
  • Example 1 - Example 3 the inventors of the present invention conducted experiments with reference to the other materials and conditions listed in the present specification in the manners of Example 1 - Example 3, and also obtained a high sustained release rate, low dosage, and environmentally friendly carbon steel. Environmentally friendly pickling inhibitor.
  • the environmentally friendly pickling inhibitor provided by the present application is mainly prepared by a solvothermal method using aminobenzoic acid, phenylenediamine or the like as a main raw material, and has simple synthesis and no toxicity. It is easy to dissolve in acid and so on.
  • the environmentally friendly pickling inhibitor is simple to use. It can be used as a cleaning solution to pickle carbon steel by adding hydrochloric acid solution, which can effectively inhibit carbon steel in acid solution. The corrosion in the carbon steel has a high sustained release rate, low dosage and environmental protection and high efficiency.

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Abstract

一种环境友好型酸洗缓蚀剂与其应用。所述缓蚀剂包括多芳环含氮碳量子点。所述缓蚀剂的制备方法包括：将含苯环和氨基的化合物作为反应单体与溶剂均匀混合，之后加热进行溶剂热反应，获得包含多芳环含氮碳量子点的酸洗缓蚀剂。该酸洗缓蚀剂具有合成简单、无毒无害、易溶于酸等特点；同时使用方法简单，加入盐酸溶液中即可作为清洗液对碳钢进行酸洗，可有效的抑制碳钢在酸液中的腐蚀，对碳钢缓释率高，且用量低、环保高效。

Description

环境友好型酸洗缓蚀剂与其应用 技术领域
本申请涉及一种缓蚀剂，特别涉及一种环保的用于碳钢酸洗的多芳环含氮碳量子点酸洗缓蚀剂及其制备方法与应用，属于金属防腐技术领域。
背景技术
酸洗是清除金属材料表面污垢和锈蚀的一种低廉、简单有效的方法。在酸洗过程中，最常用的酸主要有盐酸和硫酸，而盐酸是使用最广的酸洗剂；然而在清洗过程中，盐酸会对金属材料具有很强的腐蚀性，产生过蚀现象；除此之外，盐酸与金属反应产生的氢气会导致金属材料发生氢脆腐蚀，同时氢气的产生会带出大量酸雾，恶化劳动条件。因此，在酸洗过程中需要添加缓蚀剂来降低金属材料的腐蚀以及酸雾的挥发。
目前常用的缓蚀剂主要包括无机缓蚀剂和有机缓蚀剂。传统的无机缓蚀剂主要包括亚硝酸盐和铬酸盐，但是此类缓蚀剂会对人、动物以及生态环境产生极大地危害；而含磷、硫等的有机缓蚀剂等虽然具有良好的缓释效果，但同样会对环境具有很大的危害。因此，随着人类环保意识的提高和可持续发展思想的提出，发展无毒高效的环境友好型缓蚀剂成为研究缓蚀剂的一个新的方向。
发明内容
本申请的主要目的在于提供一种环境友好型酸洗缓蚀剂与其应用，以克服现有技术的不足。
为实现前述发明目的，本申请采用的技术方案包括：
本申请实施例提供了多芳环含氮碳量子点于制备酸洗缓蚀剂中的应用。
其中优选的，所述多芳环含氮碳量子点的粒径为3～4nm。
优选的，所述多芳环含氮碳量子点的组成元素包括C、N和O。
在一些优选实施方案之中，所述多芳环含氮碳量子点的制备方法包括：
将反应单体与溶剂均匀混合，之后加热进行溶剂热反应，发生分子之间的脱水、脱羧以及键合，获得多芳环含氮碳量子点。
其中，所述反应单体包括含苯环和氨基的化合物。
进一步的，所述反应单体包括氨基苯甲酸类化合物和/或苯二胺类化合物。
进一步的，所述反应单体包括4-氨基水杨酸、5-氨基水杨酸、邻苯二胺、对苯二胺和间苯二胺中的任意一种或两种以上的组合。
在一些实施例中，所述溶剂热反应的温度为180～200℃，时间为12～18h。
进一步的，所述溶剂与反应单体的体积质量比为5mL：0.1g～20mL：0.1g，优选为5mL：0.1g～10mL：0.1g。
本申请实施例还提供了一种环境友好型酸洗缓蚀剂，所述缓蚀剂包括多芳环含氮碳量子点。
其中优选的，所述多芳环含氮碳量子点的粒径为3～4nm。
优选的，所述多芳环含氮碳量子点的组成元素包括C、N和O。
本申请实施例还提供了前述的环境友好型酸洗缓蚀剂于金属防蚀领域的应用。
进一步的，所述应用包括：在对金属材料进行酸洗之前，在酸洗剂中加入所述环境友好型酸洗缓蚀剂，其中，所述环境友好型酸洗缓蚀剂的添加浓度为0～200mg·L-1。
本申请实施例还提供了一种金属材料的酸洗方法，其包括：以含有前述的环境友好型酸洗缓蚀剂的酸洗剂对金属材料进行清洗。
与现有技术相比，本申请提供的环境友好型酸洗缓蚀剂包括多芳环含氮碳量子点。所述多芳环含氮碳量子点主要以氨基苯甲酸、苯二胺等为主要原料通过溶剂热方法制得，具有合成简单、无毒无害、易溶于酸等特点；同时所获的包含有多芳环含氮碳量子点的酸洗缓蚀剂使用方法简单，加入盐酸溶液中即可作为清洗液对碳钢进行酸洗，可有效的抑制碳钢在酸液中的腐蚀，对碳钢缓释率高，且用量低、环保高效。
附图说明
图1a、图1b分别为本申请实施例1所获环境友好型酸洗缓蚀剂中的多芳环含氮碳量 子点的TEM、SPM形貌图；
图1c、图1d、图1e分别对应于图1b中三条曲线经过的多芳环含氮碳量子点的二维轮廓图；
图1f为本申请实施例1中4-氨基水杨酸与所制备的多芳环含氮碳量子点的XPS光谱图；
图2为本申请实施例1中以含有不同浓度的环境友好型酸洗缓蚀剂的1mol·L-1HCl溶液对碳钢浸泡0.5h后的极化曲线图；
图3为本申请实施例1中在最佳缓蚀剂浓度(10mg L-1)下，缓蚀效率随浸泡时间的变化曲线图；
图4a为本申请实施例1中Q235碳钢在缓蚀剂浓度为1mol·L-1的盐酸溶液中浸泡72小时后的扫描电镜图；
图4b为本申请实施例1中Q235碳钢在缓蚀剂浓度为10mg L-1的盐酸溶液中浸泡72小时后的扫描电镜图；
图5为本申请实施例2中以含有不同浓度的环境友好型酸洗缓蚀剂的1mol·L-1HCl溶液对碳钢浸泡0.5h后的极化曲线图；
图6为本申请实施例2中在最佳缓蚀剂浓度(200mg L-1)下，缓蚀效率随浸泡时间的变化曲线图；
图7为本申请实施例2中Q235碳钢在缓蚀剂浓度为200mg L-1的盐酸溶液中浸泡72小时后的扫描电镜图；
图8为本申请实施例3中以含有不同浓度的环境友好型酸洗缓蚀剂的1mol·L-1HCl溶液对碳钢浸泡72h后的极化曲线图；
图9为本申请实施例3中在最佳缓蚀剂浓度(200mg L-1)下，缓蚀效率随浸泡时间的变化曲线图；
图10为本申请实施例3中Q235碳钢在缓蚀剂浓度为200mg L-1的盐酸溶液中浸泡72小时后的扫描电镜图。
具体实施方式
近年来，碳量子点在纳米材料领域引起了广泛的研究热潮，其荧光性好、水溶性、毒性低，这些特点使得碳量子点在生物传感领域具有很高的应用价值。业界研发人员已报道了通过将4-氨基水杨酸溶剂热处理后成功制备荧光性好、低毒的含氮碳量子点；同样报道了苯二胺溶剂热处理后同样表现出很好地荧光性和细胞相容性。通过对比我们可以发现，这两种碳量子点都具有苯环和氮原子；而具有该结构的缓释剂通常会与金属表面产生一定的物理化学作用，降低金属的腐蚀。
鉴于现有技术中的不足，本案发明人经长期研究和大量实践，得以提出本申请的技术方案，主要是以氨基苯甲酸、苯二胺为主要原料通过溶剂热方法制得包含有多芳环含氮碳量子点的环境友好型酸洗缓蚀剂。如下将对该技术方案、其实施过程及原理等作进一步的解释说明。
本申请实施例的一个方面提供的多芳环含氮碳量子点于制备酸洗缓蚀剂中的应用。
其中，所述多芳环含氮碳量子点的粒径为3～4nm。
优选的，所述多芳环含氮碳量子点的组成元素包括C、N和O。
在一些优选实施方案之中，所述多芳环含氮碳量子点的制备方法包括：
将反应单体与溶剂均匀混合，之后加热进行溶剂热反应，发生分子之间的脱水、脱羧以及键合，最终获得多芳环含氮碳量子点。
其中，所述反应单体包括含苯环和氨基的化合物。
在一些优选实施方案之中，所述反应单体包括氨基苯甲酸类化合物和/或苯二胺类化合物。
进一步的，所述反应单体选自4-氨基水杨酸、5-氨基水杨酸、邻苯二胺、对苯二胺和间苯二胺等中的任意一种或两种以上的组合，但不限于此。
在一些实施例中，所述溶剂热反应的温度为180～200℃，时间为12～18h。
进一步的，所述溶剂与反应单体的体积质量比(亦可以称为液固比)范围为5mL：0.1g～20mL：0.1g，优选体积质量比为5mL：0.1g～10mL：0.1g。
进一步的，所述溶剂选自乙醇。
进一步的，所述多芳环含氮碳量子点的制备方法还包括：反应结束后，将反应体系置于截留分子量为1.0kDa～5.0kDa的透析袋中提纯，之后除去溶剂，干燥，获得所述多 芳环含氮碳量子点。
优选的，所述透析袋的截留分子量为1.0kDa～3.0kDa。
其中，在一些较为具体的实施方案中，所述多芳环含氮碳量子点的制备方法可以包括：
a.取原料溶于适量的无水乙醇，在200℃下加热18小时，所述原料包括4-氨基水杨酸、5-氨基水杨酸、邻苯二胺、对苯二胺、间苯二胺、以及其它含苯环/氨基的单体。
b.反应完毕，将反应溶液置于3.0kDa的透析袋中进行提纯，除去未反应的原料。
c.将提纯后的产物离心除去溶剂，真空干燥，获得所述多芳环含氮碳量子点。
本申请实施例的另一个方面提供了一种环境友好型酸洗缓蚀剂，所述缓蚀剂包括多芳环含氮碳量子点。
优选的，所述多芳环含氮碳量子点的粒径为3～4nm。
优选的，所述多芳环含氮碳量子点的组成元素包括C、N和O。
在一些优选实施方案之中，所述多芳环含氮碳量子点的制备方法包括：
将反应单体与溶剂均匀混合，之后加热进行溶剂热反应，获得多芳环含氮碳量子点。
其中，所述反应单体包括含苯环和氨基的化合物。
在一些优选实施方案之中，所述反应单体包括氨基苯甲酸类化合物和/或苯二胺类化合物。
进一步的，所述反应单体选自4-氨基水杨酸、5-氨基水杨酸、邻苯二胺、对苯二胺和间苯二胺等中的任意一种或两种以上的组合，但不限于此。
在一些实施例中，所述溶剂热反应的温度为180～200℃，时间为12～18h。
进一步的，所述溶剂与反应单体的体积质量比(亦可以称为液固比)范围为5mL：0.1g～20mL：0.1g，优选体积质量比为5mL：0.1g～10mL：0.1g。
进一步的，所述溶剂选自乙醇。
进一步的，所述多芳环含氮碳量子点的制备方法还包括：反应结束后，将反应体系置于截留分子量为1.0～5.0kDa的透析袋中提纯，之后除去溶剂，干燥，获得所述多芳环含氮碳量子点，其中优选的透析袋截留分子量为1.0～3.0kDa。
本申请实施例的另一个方面还提供了前述的环境友好型酸洗缓蚀剂的用途，特别是 在金属防蚀领域的应用。
进一步的，所述应用包括：在对金属材料进行酸洗之前，在酸洗剂中加入所述环境友好型酸洗缓蚀剂，其中，所述环境友好型酸洗缓蚀剂的添加浓度为0～200mg·L-1。
优选的，所述酸洗剂包括盐酸。
本申请实施例的另一个方面还提供了一种金属材料的酸洗方法，其包括：以含有前述的环境友好型酸洗缓蚀剂的酸洗剂对金属材料进行清洗。
优选的，所述金属材料包括碳钢等，但不限于此。
本申请所获环境友好型酸洗缓蚀剂可以进行金属防腐的原理在于：溶剂热方法制得的多芳环含氮碳量子点与碳钢表面相互作用，在碳钢表面形成一层吸附层，从而可以减缓金属的腐蚀。
下面结合实施例及附图对本申请的技术方案做进一步详细说明，但本申请并不仅仅局限于下述实施例。
本申请以下实施例采用的缓蚀性能评价标准及方法如下：
1、GB10124-88《金属材料实验室均匀腐蚀全浸试验方法》进行失重试验；
2、扫描电镜用于观察腐蚀形貌。
实施例1
1.将0.6g 4-氨基水杨酸溶解于60mL无水乙醇中，然后在200℃下加热18h。反应完毕，将反应溶液置于3.0kDa的透析袋中进行提纯，除去未反应的原料。将提纯后的产物离心除去溶剂，真空干燥，获得多芳环含氮碳量子点，其TEM和SPM形貌图可分别参考图1a和图1b，可以观察到多芳环含氮碳量子点的尺寸约为3～4nm(如图1c、图1d、图1e)，且主要由C、N、O三种元素组成(如图1f)。将所获多芳环含氮碳量子点制备形成环境友好型酸洗缓蚀剂。
2.将Q235碳钢钢片浸入1mol·L-1盐酸溶液中，并加入本实施例制备的环境友好型酸洗缓蚀剂，使缓蚀剂浓度分别为0mg·L-1，1mg·L-1，5mg·L-1，10mg·L-1，50mg·L-1，100mg·L-1，在室温下浸泡0.5小时进行极化测试。
极化测试结果如图2所示，不同缓蚀剂浓度下的缓蚀效率分别为0，12.3％，86.7％，90.9％，89.3％，87.2％，由此可看出最大缓蚀率的浓度为10mg·L-1。
3.将Q235碳钢钢片浸入1mol·L-1盐酸溶液中，加入本实施例制备的环境友好型酸洗缓蚀剂浓度为具有最大缓蚀率的浓度，即10mg·L-1，在室温下浸泡72小时，缓蚀效率随浸泡时间的变化曲线图如图3所示。
(1)失重法测试结果：缓蚀剂浓度为10mg·L-1，浸泡72小时后，缓蚀效率为94％。
(2)通过扫描电镜观察结果：72小时后，浸泡在1mol·L-1盐酸溶液中的Q235碳钢钢片已经发生严重的腐蚀，参见图4a所示；而加入的缓蚀剂浓度为10mg·L-1的盐酸溶液中浸泡的Q235碳钢表面腐蚀相对较轻，但是抛光产生的划痕由于腐蚀已经消失，可参见图4b所示。
实施例2
1.将0.6g对苯二胺溶解于60mL无水乙醇中，然后在180℃下加热12h。反应完毕，将反应溶液置于3.0kDa的透析袋中进行提纯，除去未反应的原料。将提纯后的产物离心除去溶剂，真空干燥，获得多芳环含氮碳量子点。将所获多芳环含氮碳量子点制备形成环境友好型酸洗缓蚀剂。
2.将Q235碳钢钢片浸入1mol·L-1盐酸溶液中，并加入本实施例制备的环境友好型酸洗缓蚀剂，使缓蚀剂浓度分别为0mg·L-1，10mg·L-1，50mg·L-1，100mg·L-1，200mg·L-1，在室温下浸泡0.5小时进行极化测试。
极化测试结果如图5所示，不同缓蚀剂浓度下的缓释效率分别为0，71％，86％，88％，88％。
3.将Q235碳钢钢片浸入1mol·L-1盐酸溶液中，加入本实施例制备的环境友好型酸洗缓蚀剂浓度为具有最大缓蚀率的浓度，即200mg·L-1，在室温下浸泡72小时，缓蚀效率随浸泡时间的变化曲线图如图6所示。
(1)失重法测试结果：缓蚀剂浓度为200mg·L-1，浸泡88小时后，缓蚀效率为97.1％。
(2)通过扫描电镜观察结果：72小时后，浸泡在1mol·L-1盐酸溶液中的Q235碳钢钢片已经发生严重的腐蚀；而加入的缓蚀剂浓度为200mg·L-1的盐酸溶液中浸泡的Q235碳钢表面腐蚀相对较轻，表面抛光划痕依然存在，如图7所示。
实施例3
1.将0.6g间苯二胺溶解于60mL无水乙醇中，然后在180℃下加热12h。反应完 毕，将反应溶液置于3.0kDa的透析袋中进行提纯，除去未反应的原料。将提纯后的产物离心除去溶剂，真空干燥，获得多芳环含氮碳量子点。将所获多芳环含氮碳量子点制备形成环境友好型酸洗缓蚀剂。
2.将Q235碳钢钢片浸入1mol·L-1盐酸溶液中，并加入本实施例制备的环境友好型酸洗缓蚀剂，使缓蚀剂浓度分别为0mg·L-1，10mg·L-1，50mg·L-1，100mg·L-1，200mg·L-1，在室温下浸泡72小时进行极化测试。
极化测试结果如图8所示，不同缓蚀剂浓度下的缓释效率分别为0，0，73％，89％，94％。
3.将Q235碳钢钢片浸入1mol·L-1盐酸溶液中，加入本实施例制备的环境友好型酸洗缓蚀剂浓度为具有最大缓蚀率的浓度，即200mg·L-1，在室温下浸泡72小时，缓蚀效率随浸泡时间的变化曲线图如图9所示。
(1)失重法测试结果：缓蚀剂浓度为200mg·L-1，浸泡88小时后，缓蚀效率为99.0％。
(2)通过扫描电镜观察结果：72小时后，浸泡在含200mg·L-1缓蚀剂的盐酸溶液中的Q235碳钢钢片的扫描电镜图如图10所示。
此外，本案发明人还参照实施例1-实施例3的方式，以本说明书中列出的其它原料和条件等进行了试验，并同样制得了对碳钢缓释率高、用量低且环保高效的环境友好型酸洗缓蚀剂。
综上所述，藉由上述技术方案，本申请提供的环境友好型酸洗缓蚀剂主要以氨基苯甲酸、苯二胺等为主要原料通过溶剂热方法制得，具有合成简单、无毒无害、易溶于酸等特点；同时所获的环境友好型酸洗缓蚀剂使用方法简单，加入盐酸溶液中即可作为清洗液对碳钢进行酸洗，可有效的抑制碳钢在酸液中的腐蚀，对碳钢缓释率高，用量低且环保高效。
应当理解，上述实施例仅为说明本申请的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本申请的内容并据以实施，并不能以此限制本申请的保护范围。例如，在本说明书中未述及的部分采取或借鉴已有技术即可实现，因此凡根据本申请精神实质所作的等效变化或修饰，都应涵盖在本申请的保护范围之内。

Claims (29)

  1. 多芳环含氮碳量子点于制备酸洗缓蚀剂中的应用。
  2. 根据权利要求1所述的应用，其特征在于：所述多芳环含氮碳量子点的粒径为3～4nm。
  3. 根据权利要求1所述的应用，其特征在于：所述多芳环含氮碳量子点的组成元素包括C、N和O。
  4. 根据权利要求1所述的应用，其特征在于：所述多芳环含氮碳量子点的制备方法包括：将反应单体与溶剂均匀混合，之后加热进行溶剂热反应，最终获得多芳环含氮碳量子点；其中，所述反应单体包括含苯环和氨基的化合物。
  5. 根据权利要求4所述的应用，其特征在于：所述反应单体包括氨基苯甲酸类化合物和/或苯二胺类化合物。
  6. 根据权利要求5所述的应用，其特征在于：所述反应单体包括4-氨基水杨酸、5-氨基水杨酸、邻苯二胺、对苯二胺和间苯二胺中的任意一种或两种以上的组合。
  7. 根据权利要求4所述的应用，其特征在于：所述溶剂与反应单体的体积质量比范围为5mL：0.1g～20mL：0.1g。
  8. 根据权利要求7所述的应用，其特征在于：所述溶剂与反应单体的体积质量比范围为5mL：0.1g～10mL：0.1g。
  9. 根据权利要求4所述的应用，其特征在于：所述溶剂包括乙醇。
  10. 根据权利要求4所述的应用，其特征在于：所述溶剂热反应的温度为180～200℃，时间为12～18h。
  11. 根据权利要求4所述的应用，其特征在于还包括：在所述的溶剂热反应结束后，将所获的混合反应体系置于截留分子量为1.0kDa～5.0kDa的透析袋中提纯，之后除去溶剂，干燥，获得所述多芳环含氮碳量子点。
  12. 根据权利要求11所述的应用，其特征在于：所述透析袋的截留分子量为1.0kDa～3.0kDa。
  13. 一种环境友好型酸洗缓蚀剂，其特征在于：所述缓蚀剂包括多芳环含氮碳量子 点。
  14. 根据权利要求13所述的环境友好型酸洗缓蚀剂，其特征在于：所述多芳环含氮碳量子点的粒径为3～4nm。
  15. 根据权利要求13所述的环境友好型酸洗缓蚀剂，其特征在于：所述多芳环含氮碳量子点的组成元素包括C、N和O。
  16. 根据权利要求13所述的环境友好型酸洗缓蚀剂，其特征在于，所述多芳环含氮碳量子点的制备方法包括：将反应单体与溶剂均匀混合，之后加热进行溶剂热反应，获得多芳环含氮碳量子点；其中，所述反应单体包括含苯环和氨基的化合物。
  17. 根据权利要求16所述的环境友好型酸洗缓蚀剂，其特征在于：所述反应单体包括氨基苯甲酸类化合物和/或苯二胺类化合物。
  18. 根据权利要求17所述的环境友好型酸洗缓蚀剂，其特征在于：所述反应单体包括4-氨基水杨酸、5-氨基水杨酸、邻苯二胺、对苯二胺和间苯二胺中的任意一种或两种以上的组合。
  19. 根据权利要求16所述的环境友好型酸洗缓蚀剂，其特征在于：所述溶剂与反应单体的体积质量比范围为5mL：0.1g～20mL：0.1g。
  20. 根据权利要求19所述的环境友好型酸洗缓蚀剂，其特征在于：所述溶剂与反应单体的体积质量比范围为5mL：0.1g～10mL：0.1g。
  21. 根据权利要求16所述的环境友好型酸洗缓蚀剂，其特征在于：所述溶剂包括乙醇。
  22. 根据权利要求16所述的环境友好型酸洗缓蚀剂，其特征在于：所述溶剂热反应的温度为180～200℃，时间为12～18h。
  23. 根据权利要求16所述的环境友好型酸洗缓蚀剂，其特征在于还包括：在所述的溶剂热反应结束后，将所获的混合反应体系置于截留分子量为1.0kDa～5.0kDa的透析袋中提纯，之后除去溶剂，干燥，获得所述多芳环含氮碳量子点。
  24. 根据权利要求23所述的环境友好型酸洗缓蚀剂，其特征在于：所述透析袋的截留分子量为1.0kDa～3.0kDa。
  25. 权利要求13-24中任一项所述的环境友好型酸洗缓蚀剂于金属防蚀领域的应用。
  26. 根据权利要求25所述的应用，其特征在于包括：在对金属材料进行酸洗之前，在酸洗剂中加入所述环境友好型酸洗缓蚀剂，其中，所述环境友好型酸洗缓蚀剂的添加浓度为0～200mg·L-1。
  27. 根据权利要求26所述的应用，其特征在于：所述酸洗剂包括盐酸。
  28. 一种金属材料的酸洗方法，其特征在于包括：以含有权利要求13-24中任一项所述的环境友好型酸洗缓蚀剂的酸洗剂对金属材料进行清洗。
  29. 根据权利要求28所述的金属材料的酸洗方法，其特征在于：所述金属材料包括碳钢。
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