CN105200483A - Mid-temperature treatment aluminum alloy anode oxide film nickel-free hole sealing agent and preparation method thereof - Google Patents

Abstract

The invention discloses a mid-temperature treatment aluminum alloy anode oxide film nickel-free hole sealing agent. The mid-temperature treatment aluminum alloy anode oxide film nickel-free hole sealing agent is prepared from, by weight, 8-8.5 parts of magnesium acetate, 19-20 parts of triethanolamine, 3-3.2 parts of ammonium acetate, an adequate amount of deionized water, 1.1-1.2 parts of potassium fluotitanate, 0.04-0.07 part of cyclohexanone, 0.05-0.06 part of isoamyl alcohol, 0.4-0.5 part of lithium silicate, 2.6-2.8 parts of dodecafluoroheptylpropyltrimethoxysilane, 1-1.2 parts of tetrabutyl titanate, 45-48 parts of ethyl alcohol, 8.6-9 parts of ammonium hydroxide and 0.3-0.4 part of fluorine-containing surfactants. According to the hole sealing agent, the permeability, the caking property and the hydrophobicity are achieved, and the hole sealing effect is improved; meanwhile, the oxidation resistance and the the anti-interference performance to SO4<2-> of an oxide film are improved; due to the fact that the potassium fluotitanate, the cyclohexanone and the isoamyl alcohol are used, the treatment temperature is decreased, the treatment efficiency is improved, the treated oxide film is good in sealing performance, and the energy consumption is reduced.

Description

A kind of heat-treated under medium temperature aluminium alloy anode oxide film is without nickel hole sealing agent and preparation method thereof

Technical field

The present invention relates to aluminium alloy anode oxide film without nickel hole sealing agent technical field, particularly relate to a kind of heat-treated under medium temperature aluminium alloy anode oxide film without nickel hole sealing agent and preparation method thereof.

Background technology

At present, Aluminum-aluminum alloy generally adopts anodized surface guard technology, certain thickness oxide film is formed on Aluminum-aluminum alloy surface, there is a large amount of micropore in the surface due to oxide film, must suitable sealing treatment be carried out, common enclosure method mainly contain boiling water (or steam) close, nickel salt close, macromolecule resin close.Boiling water (or steam) enclosure method energy consumption is high and cannot meet the requirement compared with high anti-corrosion; Conventional nickel salt encapsulant is containing Ni ²⁺, F ^-to human body and the effect of environmental toxic evil, its stripping quantity is subject to the strict restriction of the regulations such as European Union 94/27/EEC nickel instruction; The molecular volume of macromolecule resin is too large, cannot diffuse into pore interior and realize good closed performance.Therefore, the demand energy-efficient, the green aluminum anodized film sealing technique of asepsis environment-protecting is developed is urgent, wherein, the hole sealing agent being main component with an alkali metal salt or alkaline earth salt has the characteristics such as resource is wide, with low cost, environmental friendliness, is a kind of novel green anode oxide film hole sealing agent.The U.S., Wuhan Inst. of Material Protection of China have successively carried out the technical study of alkaline earth salt sealing of hole." 6063 aluminium alloy anode oxide films are without the optimization of nickel hole-sealing technology " literary composition take magnesium acetate as hole sealing agent main component, orthogonal experiment is adopted to have studied the impact of hole-sealing technology parameter on sealing quality, obtain the Optimization Technology without nickel hole sealing technology, and the technique applied research of anti-ion interference has been carried out to this technique.Result shows, can the realizing in 80 DEG C antianode oxide film under temperature without nickel hole-sealing technology and carry out sealing pores of optimization, and sealing quality is good, anti-Na ⁺interference performance is given prominence to, and achieves sealing of hole process without Ni ²⁺deng environomental pollution source, environmental protection, and the reduction of sealing of hole temperature is conducive to reducing energy consumption, and energy-saving benefit is remarkable.But this technique still has weak point, anti-SO ₄ ^2-disturb poor, and perviousness is bad, the space closure of the oxide film bottom of bottom is bad, also there is the problem that the performances such as germ resistance, solidity to corrosion, thermotolerance, salt fog resistance, wear resistance, oxidation-resistance are not good, and the toughness of encapsulant, hardness, shrinking percentage etc. also can affect closure, need to improve.

Summary of the invention

The object of the invention is exactly the defect in order to make up prior art, provides a kind of heat-treated under medium temperature aluminium alloy anode oxide film without nickel hole sealing agent and preparation method thereof.

The present invention is achieved by the following technical solutions:

A kind of heat-treated under medium temperature aluminium alloy anode oxide film, without nickel hole sealing agent, is made up of the raw material of following weight part: magnesium acetate 8-8.5, trolamine 19-20, ammonium acetate 3-3.2, deionized water are appropriate, potassium fluotitanate 1.1-1.2, pimelinketone 0.04-0.07, primary isoamyl alcohol 0.05-0.06, lithium silicate 0.4-0.5, ten difluoro heptyl propyl trimethoxy silicane 2.6-2.8, tetrabutyl titanate 1-1.2, ethanol 45-48, ammoniacal liquor 8.6-9, fluorochemical surfactant 0.3-0.4.

Described heat-treated under medium temperature aluminium alloy anode oxide film, without the preparation method of nickel hole sealing agent, comprises the following steps:

(1) by tetrabutyl titanate, ethanol mixing, stirring obtains tetrabutyl titanate ethanolic soln, by lithium silicate, ten difluoro heptyl propyl trimethoxy silicanes, fluorochemical surfactant mixing, the water adding 5-6 weight part stirs, obtain solution, to instill in tetrabutyl titanate ethanolic soln under described solution stirring, 1.5-1.8h is stirred under 250-300r/min condition, obtain mixture, then ammoniacal liquor is slowly dripped in people's said mixture, at 30-35 DEG C, obtain emulsion after stirring reaction 3-3.5h;

(2) mixing solutions is prepared, magnesium acetate 8g/L, trolamine 19g/L, ammonium acetate 3g/L;

(3) emulsion (1) step obtained adds in the solution that (2) step obtains by 1.6-1.8g/L, then adds other remaining component, mixes, and regulates pH=5, is heated to 60-65 DEG C, aluminium section bar is flooded 18-22min, to obtain final product.

Advantage of the present invention is: the present invention uses tetrabutyl titanate to form nano titanium oxide, employ lithium silicate, ten difluoro heptyl propyl trimethoxy silicanes, fluorochemical surfactant simultaneously, through reaction, the perviousness of hole sealing agent, cohesiveness, hydrophobicity can be improved, improve sealing of hole effect, improve the oxidation-resistance of oxide film and anti-SO simultaneously ₄ ^2-interference; By using potassium fluotitanate, pimelinketone, primary isoamyl alcohol, reducing treatment temp, improve processing efficiency, the oxide film good airproof performance after process, save energy consumption.

Embodiment

A kind of heat-treated under medium temperature aluminium alloy anode oxide film, without nickel hole sealing agent, is made up of the raw material of following weight part (kilogram): magnesium acetate 8, trolamine 19, ammonium acetate 3, deionized water are appropriate, potassium fluotitanate 1.1, pimelinketone 0.04, primary isoamyl alcohol 0.05, lithium silicate 0.4, ten difluoro heptyl propyl trimethoxy silicane 2.6, tetrabutyl titanate 1, ethanol 45, ammoniacal liquor 8.6, fluorochemical surfactant 0.3.

Described heat-treated under medium temperature aluminium alloy anode oxide film, without the preparation method of nickel hole sealing agent, comprises the following steps:

(1) by tetrabutyl titanate, ethanol mixing, stirring obtains tetrabutyl titanate ethanolic soln, by lithium silicate, ten difluoro heptyl propyl trimethoxy silicanes, fluorochemical surfactant mixing, the water adding 5 weight parts stirs, and obtains solution, will instill in tetrabutyl titanate ethanolic soln under described solution stirring, 1.5h is stirred under 250r/min condition, obtain mixture, then ammoniacal liquor is slowly dripped in people's said mixture, at 30 DEG C, obtain emulsion after stirring reaction 3h;

(2) mixing solutions is prepared, magnesium acetate 8g/L, trolamine 19g/L, ammonium acetate 3g/L;

(3) emulsion (1) step obtained adds in the solution that (2) step obtains by 1.6g/L, then adds other remaining component, mixes, and regulates pH=5, is heated to 60 DEG C, aluminium section bar is flooded 18min, to obtain final product.

Experimental data:

Detect according to GB/T8753.2-2005, sealing of hole weightlessness is 20.2mg/dm ²; According to GB/T8753.4-2005, dyeing grade is 0, and anti-dye high adsorption capacity, illustrates that seal quality is qualified.

Studied by anti-ion interference, even if when result display Na+ content increases to 400mg/L, sealing of hole weightlessness is also only 22.3mg/dm ², be less than 30mg/dm ², sealing quality is good, and anti-Na+ interference performance is given prominence to; Work as SO ₄ ^2-content when being 500mg/L, sealing of hole weightlessness is 26.3mg/dm ², be less than 30mg/dm ², sealing of hole effect is better, anti-SO ₄ ^2-disturb.

By carrying out electron-microscope scanning to oxide film surface, see that a large amount of micropores on the surface of oxide film are nearly all closed, pore space structure is few, and sealing of hole is comparatively even.

Claims (2)

1. heat-treated under medium temperature aluminium alloy anode oxide film is without a nickel hole sealing agent, it is characterized in that being made up of the raw material of following weight part: magnesium acetate 8-8.5, trolamine 19-20, ammonium acetate 3-3.2, deionized water are appropriate, potassium fluotitanate 1.1-1.2, pimelinketone 0.04-0.07, primary isoamyl alcohol 0.05-0.06, lithium silicate 0.4-0.5, ten difluoro heptyl propyl trimethoxy silicane 2.6-2.8, tetrabutyl titanate 1-1.2, ethanol 45-48, ammoniacal liquor 8.6-9, fluorochemical surfactant 0.3-0.4.

2. heat-treated under medium temperature aluminium alloy anode oxide film according to claim 1 is without the preparation method of nickel hole sealing agent, it is characterized in that comprising the following steps:

(1) by tetrabutyl titanate, ethanol mixing, stirring obtains tetrabutyl titanate ethanolic soln, by lithium silicate, ten difluoro heptyl propyl trimethoxy silicanes, fluorochemical surfactant mixing, the water adding 5-6 weight part stirs, obtain solution, to instill in tetrabutyl titanate ethanolic soln under described solution stirring, 1.5-1.8h is stirred under 250-300r/min condition, obtain mixture, then ammoniacal liquor is slowly dripped in people's said mixture, at 30-35 DEG C, obtain emulsion after stirring reaction 3-3.5h;

(2) mixing solutions is prepared, magnesium acetate 8g/L, trolamine 19g/L, ammonium acetate 3g/L;

(3) emulsion (1) step obtained adds in the solution that (2) step obtains by 1.6-1.8g/L, then adds other remaining component, mixes, and regulates pH=5, is heated to 60-65 DEG C, aluminium section bar is flooded 18-22min, to obtain final product.