阅读说明：本技术 一种钛粉表面活化剂及其使用方法 (Titanium powder surface active agent and use method thereof ) 是由 王胜民 赵晓军 张俊 裴和中 何明奕 苑振涛 于 2019-11-18 设计创作，主要内容包括：本发明公开了一种钛粉表面活化剂及其使用方法,属于钢铁基体镀钛技术领域。本发明的钛粉表面活化剂中各原料及其质量百分比为：氟化氢铵8%~20%,硫酸锌(ZnSO<Sub>4</Sub>·7H<Sub>2</Sub>O)5%~10%,聚乙二醇6%~15%,氨基磺酸镍3%~8%,乳化剂3%~10%,草酸5%~10%,次亚磷酸钠2%~5%,无机强酸0.5%~5%和余量水。本发明所述表面活化剂用于钢铁基体上的机械镀钛,使用时各组分按一定顺序添加配制,按计算量加入使用,加入后能够保证镀液环境中钛粉活化效果好,活化稳定,保障钛粉的连续吸附、沉积,获得理想的镀钛层。(The invention discloses a titanium powder surface active agent and a using method thereof, belonging to the technical field of titanium plating of steel matrixes. The titanium powder surface activator comprises the following raw materials in percentage by mass: 8-20% of ammonium bifluoride and zinc sulfate (ZnSO) 4 ·7H 2 5-10% of O), 6-15% of polyethylene glycol, 3-8% of nickel sulfamate, 3-10% of emulsifier, 5-10% of oxalic acid, 2-5% of sodium hypophosphite, 0.5-5% of inorganic strong acid and the balance of water. The surface active agent is used for mechanical titanium plating on a steel matrix, when in use, the components are added and prepared in a certain sequence and are added according to calculated amount, and after the surface active agent is added, the titanium powder in a plating solution environment can be ensured to have good activation effect and stable activation, the continuous adsorption and deposition of the titanium powder are ensured, and an ideal titanium plating layer is obtained.)

1. A titanium powder surfactant is characterized in that: the activating agent is prepared from the following raw materials in percentage by mass: 8-20% of ammonium bifluoride and zinc sulfate (ZnSO)₄·7H₂5-10% of O), 6-15% of polyethylene glycol, 3-8% of nickel sulfamate, 3-10% of emulsifier, 5-10% of oxalic acid, 2-5% of sodium hypophosphite, 0.5-5% of inorganic strong acid and the balance of water.

2. The titanium powder surfactant according to claim 1, wherein: the inorganic strong acid is industrial concentrated sulfuric acid or hydrofluoric acid.

3. The titanium powder surfactant according to claim 1, wherein: the emulsifier is OP-10 or TX-10.

4. The titanium powder surfactant as set forth in claim 1 for use in a method of preparing a mechanical titanium plating layer comprising the steps of pre-treating to remove surface contamination of a workpiece, charging, titanizing and post-treating, characterized in that: in the process of titanium plating, firstly, titanium powder is added into the plating solution, then an activating agent is added into the plating solution immediately, or the titanium powder and the activating agent are firstly mixed and immediately added into the plating solution.

5. The method of claim 4, further comprising: the activator is added at the time of useQ _H With the addition of titanium powderQ _Ti The relationship between them is:Q _H =(0.6~0.9)×Q _Ti whereinQ _H The unit of (a) is in ml,Q _Ti the bit is g.

Technical Field

The invention relates to a titanium powder surface activator and a using method thereof, belonging to the technical field of surface protection, in particular to the technical field of titanium powder mechanical plating.

Background

Titanium has excellent corrosion resistance which can reach dozens of times of that of zinc and aluminum protective layers, and is very suitable for long-acting protection of steel substrates and protection in the fields of oceans and aerospace. However, because of the chemical properties of titanium, metal titanium cannot be electroplated in aqueous solution, and only molten salt electroplating, sputtering deposition and spraying can be used for coating, and only sputtering deposition is applied to the field of electronic and communication equipment with higher added value at present, while molten salt titanium plating is mostly in the research stage, and no relevant reports are found in the titanium plating technology and application of steel components, connectors, fasteners and the like.

The mechanochemical deposition is a process for forming a coating on the surface of a matrix by utilizing physical and chemical adsorption deposition and mechanical collision at normal temperature and normal pressure, compared with the traditional electroplating and hot dip plating, the mechanochemical deposition has the advantages of operation at room temperature, no hydrogen embrittlement after plating, no tempering softening and the like, and compared with the traditional electroplating electrodeposition and hot dip plating high-temperature metallurgical reaction, the mechanochemical deposition is easier to obtain various metal coatings. By taking the traditional mechanical galvanizing process and accelerator as a reference and adopting titanium powder as a raw material, scientific workers carry out a large amount of test work, but do not obtain a titanizing layer. The reason is that titanium with high corrosion resistance belongs to easily oxidized metal, the surface area of titanium powder is obviously increased along with the reduction of the particle size, and the titanium powder has stronger oxidizability, so that the surface of the commercially available metal titanium powder is covered with an oxide film with higher inertia, the oxide film is difficult to remove, and a new oxide film can be quickly formed on the cleaned titanium surface after the removal; therefore, the chemical characteristics, electrode potential, stability and the like of the surfaces of the titanium powder and the zinc powder are fundamentally different, so that the mechanochemical deposition of the titanium powder has no mature experience for reference, and the technical process is a brand-new start.

Disclosure of Invention

The invention aims to overcome the difficult problems of the current titanium plating technology, solve the problem of mechanical chemical deposition plating of titanium powder and provide a titanium powder activating agent for mechanical chemical deposition titanium plating; the activating agent is prepared from the following raw materials in percentage by mass: 8-20% of ammonium bifluoride and zinc sulfate (ZnSO)₄·7H₂5-10% of O), 6-15% of polyethylene glycol, 3-8% of nickel sulfamate, 3-10% of emulsifier, 5-10% of oxalic acid, 2-5% of sodium hypophosphite, 0.5-5% of inorganic strong acid and the balance of water, wherein the sum of the mass percentages of all the raw materials is 100%.

Preferably, the inorganic strong acid is industrial concentrated sulfuric acid or hydrofluoric acid.

Preferably, the emulsifier of the invention is OP-10 or TX-10.

The raw materials used in the invention are industrial chemical raw materials and commercial products.

The preparation process of the titanium powder surface activator comprises the following steps: firstly, adding water and inorganic strong acid into a container, then adding ammonium bifluoride, zinc sulfate, oxalic acid, nickel sulfamate, sodium hypophosphite, polyethylene glycol and an emulsifier, and uniformly stirring for use.

The invention also aims to provide a method for preparing a mechanical titanium plating layer by using the titanium powder surfactant, which specifically comprises the following steps:

(1) pretreatment: adopting a common pretreatment method for electroplating and hot dipping processes to remove grease, rust scale and the like on the surface of a workpiece;

(2) charging: putting the pretreated workpiece and a proper amount of water and glass bead medium into a plating cylinder of mechanical plating equipment, adding a small amount of sulfuric acid, and rinsing the plating cylinder for at least one time within a short time (1-2 minutes), wherein the pH value of the plating solution is 1-2; (the adding amount of water, the glass bead medium and the sulfuric acid are conventional and basically the same as that of the traditional mechanical galvanizing process)

(3) Titanium plating: before titanizing, tin salt sensitization or non-sensitization treatment can be selected; adding the weighed activator and titanium powder into a plating barrel, and rotating the plating barrel for 5-10 minutes (the activator and titanium powder can be circularly added for multiple times according to the requirement of the thickness of a plating layer in the process, wherein the time interval of circular feeding is 5-10 minutes); the adding mode can be as follows: in the process of titanium plating, firstly adding titanium powder into plating solution, and then adding an activating agent into the plating solution; or the titanium powder is first mixed with the activator and then immediately added to the plating solution.

(4) And (3) post-treatment: unloading, separating and drying.

The addition amount of the activating agent of the invention during useQ _H With the addition of titanium powderQ _Ti The relationship between them is:Q _H =(0.6~0.9)×Q _Ti whereinQ _H The unit of (a) is in ml,Q _Ti the bit is g.

The invention has the beneficial effects that:

(1) the activating agent has good activating effect, and the titanium powder with clean surface can be easily obtained in the plating solution.

After the titanium powder surface active agent is added into the plating solution, a certain content of fluorine ions and hydrogen ions can be generated in the plating solution, and oxide skin on the surface can be removed in a short time; simultaneously in Zn²⁺、Ni²⁺、Fe²⁺Under the action of the titanium powder, certain charge characteristics are formed on the surfaces of titanium powder particles, certain electric adsorption effect can be generated among the titanium powder particles and between the titanium powder and the matrix, and the adsorption between the titanium powder or titanium powder adsorption groups and the matrix and the deposition of the titanium powder on the surface of the matrix can be promoted.

(2) The activating agent of the invention has stable activation state and can realize continuous adsorption and deposition of titanium powder.

When the surface of the titanium powder is activated, the emulsifier in the activator can be quickly adsorbed to the clean surface of the titanium powder, and meanwhile, inorganic salt ions Zn in the plating solution²⁺、 Ni²⁺The oxalic acid and the high-activity points on the surface of the titanium powder are subjected to weak chemical reaction, so that the accelerated activation of the surface of the activated titanium powder particles is inhibited, the activated titanium powder is ensured to stably exist for a period of time while the surface activity is kept, and the accelerated activation of the titanium powder and even the rapid chemical reaction of the activated titanium powder in the plating solution are avoided; meanwhile, under the mechanical friction action generated by the rotation of the plating barrel, activated titanium powder can be ensured to be deposited on the surface of the substrate within a period of time (such as 5-10 min) to form a plating layer.

(3) The activating agent is convenient to use.

The additive amount of the titanium powder surfactant and the additive amount of the titanium powder are quantified, accurate addition can be realized, the stability of the additive amount of the activator is easy to ensure, and automatic metering addition is easy to realize by means of a metering pump; the adding mode can adopt titanium powder and an activating agent which are separately and simultaneously added into the plating barrel, or can adopt titanium powder added into the activating agent outside the plating barrel to be uniformly stirred and then added into the plating barrel, and the two modes can ensure the activation of the surface of the titanium powder and the stable control of the activity.

Drawings

FIG. 1 is an SEM topography of the titanium-plated layer prepared in example 7;

FIG. 2 is a scan of the composition at point 1 of FIG. 1;

FIG. 3 is a component scan map at point 2 of FIG. 1;

FIG. 4 is a scan of the composition at point 3 of FIG. 1;

FIG. 5 is a scan of the composition at point 4 of FIG. 1.

Detailed Description

The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.