CN100540736C

CN100540736C - Mg-Li alloy surface organic matter method of reducing

Info

Publication number: CN100540736C
Application number: CNB2008100641448A
Authority: CN
Inventors: 景晓燕; 卢一; 张密林
Original assignee: Harbin Engineering University
Current assignee: Harbin Engineering University
Priority date: 2008-03-21
Filing date: 2008-03-21
Publication date: 2009-09-16
Anticipated expiration: 2028-03-21
Also published as: CN101245455A

Abstract

The present invention is to provide a kind of Mg-Li alloy surface organic matter method of reducing.With a kind of in butanone, methyl phenyl ketone, ethyl benzoate, butylacetate, benzene, dimethylbenzene, phytic acid, oleic acid, alpha-naphthylamine or the Resins, epoxy is reactant; With one or both and two or more mixtures in the acetate of dilute hydrochloric acid, Virahol, dehydrated alcohol, ammonium chloride, thanomin, aniline, n-Butyl Amine 99 or 36% is promotor; According to the volume ratio of reactant and promotor 1: 1～6: 1 reactant and promotor are mixed and made into reaction soln, adjusting reacting solution pH value is 6～7, and magnesium lithium alloy is immersed in the reaction soln, is reaction 8 hours under 60 ℃ the condition in temperature.The present invention is by the reaction machine of organism at the Mg-Li alloy surface, generates the character that has, function and to the material of the influence of Mg-Li alloy surface.

Description

Mg-Li alloy surface organic matter method of reducing

(1) technical field

What the present invention relates to is a kind of surface treatment method of alloy, specifically a kind of surface treatment method of Magnuminium.

(2) background technology

Be main adding elements with Li among the Mg, promptly constituted the Mg-Li alloy, the Mg-Li alloy also has own particular performances except the characteristic that possesses general magnesium alloy; The Mg-Li alloy density is very low, is unique magnesium alloy system that is lower than magnesium matrix density, even can be lower than the density of water.The development of Mg-Li alloy material has caused that various countries pay close attention to widely, and the U.S., Germany, Japan, Korea S and China etc. have all formulated the research and development plan of Mg-Li alloy, strong promotion the development of Mg-Li alloy.The Mg-Li alloy is attracted attention by various countries as a kind of ultralight structural metallic materials of novel excellent performance, becomes the focus of research.

Metal Li is very active in the Mg-Li alloy, alloy has very high activity, can react with some functional group in the organism, organism is in characteristics such as the structure of the reaction mechanism of Mg-Li alloy surface and resultant, forms, the character that resultant has, function and to the influence of Mg-Li alloy surface etc., domestic in this respect still do not have relevant research.

(3) summary of the invention

The object of the present invention is to provide a kind of Mg-Li alloy surface organic matter method of reducing at Mg-Li reduction reaction that alloy surface organic matter carries out, change Mg-Li alloy surface composition and pattern.

The object of the present invention is achieved like this:

With a kind of in butanone, methyl phenyl ketone, ethyl benzoate, butylacetate, benzene, dimethylbenzene, phytic acid, oleic acid, alpha-naphthylamine or the Resins, epoxy is reactant; With one or both and two or more mixtures in the acetate of dilute hydrochloric acid, Virahol, dehydrated alcohol, ammonium chloride, thanomin, aniline, n-Butyl Amine 99 or 36% is promotor; Volume ratio (1: 1～6: 1) according to reactant and promotor is mixed and made into reaction soln with reactant and promotor, and adjusting reacting solution pH value is 6～7, and magnesium lithium alloy is immersed in the reaction soln, is reaction 8 hours under 60 ℃ the condition in temperature.

The XRD diffraction analysis proves: reduction reaction has all taken place on the surface of Mg-Li alloy in aromatic hydrocarbons, ketone, carboxylic acid esters.For example: ketone reductive XRD diffractogram such as Fig. 2, a finds out from figure, except going out the peak in matrix diffraction peak position, 2 θ values be the diffraction peak that occurs of 16.383,22.521,24.632,25.681,27.560,29.001,30.258 places by the standard card contrast after, find and CHLiO ₂H ₂The Partial Feature diffraction peak of O overlaps, illustrate the Mg-Li alloy is put in the mixing solutions of methyl phenyl ketone and dilute hydrochloric acid that organism is reduced, and may form the organic-inorganic composition that metal oxide and organism are connected by covalent linkage.B is for adding benzene among the figure in methyl phenyl ketone, in the reacted sample diffraction peak of Mg-Li alloy surface, basic identical with the matrix diffraction peak, just diffraction peak intensity is slightly different, the crystallization degree that matrix is described changes, may be because the material that generates is too thin at the Mg-Li alloy surface, and the material that generates form crystalline structure; C and d are respectively and add thanomin and n-Butyl Amine 99 in methyl phenyl ketones among the figure, after the reaction of Mg-Li alloy surface, without any variation, with the contrast of matrix diffraction peak, find that the peak position does not have to change substantially by the visual inspection alloy surface; The c diffraction peak intensity weakens among the figure, same explanation alloy substrate crystallization degree dies down, d is two diffraction peaks disappearances at 14.185 and 16.892 places in 2 θ values among the figure, may be because the oxide compound of magnesium and lithium has participated in the organic reducing reaction, be connected to form organic-inorganic composition with organism by covalent linkage, and this material does not have crystalline structure, so do not have the obvious diffraction peak in the drawings.

After the reduction reaction, the Infrared spectroscopy of product has proved that also aromatic hydrocarbons, ketone, carboxylic acid esters on the surface of Mg-Li alloy reduction reaction have taken place.Fig. 3 is respectively butylacetate and ethyl benzoate, scrapes the infrared spectra spectrogram of sample after the reaction of Mg-Li alloy surface.A and b are 585.8cm in wave number as seen from Figure 3 ^-1It should be 1090～1030cm in wave number for the absorption peak of lattice oxygen vibration all that more weak absorption peak appears in the place ^-1The wide slightly medium tenacity absorption peak of peak width all occurring is that C-C singly-bound and the stretching vibration of C-O singly-bound cause, is 1400～1390cm in wave number ^-1More sharp-pointed absorption peak all occurring is-CH ₃Symmetrical deformation vibration cause that among the figure a is 1590～1576cm in wave number ^-1A wide slightly medium tenacity absorption peak of peak width occurs and be in the n-Butyl Amine 99-NH ₂Formation vibration cause that among the figure b is 1549cm in wave number ^-1And 1595cm ^-1The place two more sharp-pointed weak absorption peaks occur and causes that for the C=C stretching vibration as can be seen from the figure a and b do not have absorption peak at aromatic ring structure charateristic avsorption band place, illustrate phenyl ring also hydrogenation be reduced, be 3469～3017cm in wave number ^-1The strong absorption peak that a broad occurs is in the n-Butyl Amine 99-NH ₂Stretching vibration and ethanol in-the caused stack absorption peak of OH stretching vibration, a is 3697cm in wave number among the figure ^-1The place occur a sharp-pointed medium tenacity absorption peak still for alcohol dissociates trace-OH is caused.

SEM and the energy spectrum analysis after Mg-Li alloy surface reduction reaction of aromatic hydrocarbons, ketone, carboxylic acid esters shows and generated difform product.Fig. 4 is that benzene is as the main reaction thing, Virahol and ammonium chloride are that promotor is when being 20mL benzene+10mL Virahol+5mL ammonium chloride, at the sem photograph of Mg-Li alloy surface generation organic reducing reaction back different amplification, reaction back benzene is reduced to unsaturated olefin, and Mg is oxidized to Mg (OH) ₂, simultaneous oxidation magnesium may form organic-inorganic composition by covalent linkage with organism, observes the generation that there is regular shape material such as bar-shaped grade on the surface by SEM, and more evenly and in large quantities is covered in the Mg-Li alloy surface.

(4) description of drawings

Fig. 1 is a process flow diagram of the present invention;

Fig. 2-abc is the XRD spectra of methyl phenyl ketone and differential responses promotor;

Fig. 3 is the FT-IR spectrogram of differential responses thing;

Fig. 4 is that the main reaction thing is a benzene, and Virahol and ammonium chloride are as the sem photograph of promotor, wherein: the magnification of Fig. 4-a is 5000; The magnification of Fig. 4-b is 10000.

(5) embodiment

For example the present invention is done in more detail below and describes:

The pre-treatment of Mg-Li alloy surface

In the following order the Mg-Li alloy is carried out pre-treatment: carry out grinding process with sand paper, ultrasonic cleaning 15 minutes, distilled water flushing 30 seconds is used 50g/LNaOH+15g/LNaCO ₃+ 0.5g Sodium dodecylbenzene sulfonate carries out alkali cleaning, distilled water flushing 30 seconds, and the chromic anhydride solution acid pickling of 60g/L, washing dries up at last.To carry out next step reduction reaction through after the pre-treatment at once,, not reach pretreated purpose in order to avoid Mg-Li alloy and air after handling are long duration of contact, oxidized once again.

Organic reduction reaction

Adopt pickling process, reacting solution pH value is 6～7, and temperature of reaction is 60 ℃.The main reaction thing is respectively aromatic hydrocarbons, ketone and carboxylic acid esters.

1, aromatic hydrocarbons

Through early stage pretreated Mg-Li alloy put into fast in the reaction soln that the aromatic hydrocarbons reactant that prepared and promotor mixes and go, reactant is selected benzene or dimethylbenzene for use, the volume ratio of reactant, Virahol and ammonium chloride is 3: 3: 1, grows bar-shaped, needle-like and flap at alloy surface.

2, ketone

Premenstruum pretreated Mg-Li alloy put into apace in the mixing solutions of the ketone for preparing and promotor, because promotor such as ammonium chloride and amine can promote the carrying out of organic reducing reaction, the mixed accelerators that adds after different types of promotor or the preparation has different influences to organic reducing reaction, formation and structure and morphology to resultant all have a significant impact, simultaneously can be by changing experiment condition, main reaction substrate concentration for example, promoter concentration, reaction conditionss etc. are to analyzing with a kind of reactant, the main reaction thing is selected methyl phenyl ketone for use, methyl phenyl ketone and aniline volume ratio are 4: 1, generate compact spheroidal particle at alloy surface.

3, carboxylic acid esters

Premenstruum, pretreated Mg-Li alloy will join in the mixing solutions that ester class and promotor forms fast, the different types of ester of conversion, for example contain aromatic ring and do not contain aromatic ring, simultaneously also can be by changing the kind that adds promotor, order, concentration waits is the contrast experiment, and test result is analyzed, also can change the main reaction substrate concentration, reaction conditions is similar contrast experiment, the molecular weight size has also influential to organic reaction, molecular weight helps the association of organism and Mg-Li alloy surface greatly and then reacts, the main reaction thing is selected materials such as ethyl benzoate and ethyl acetate for use, the ester class is as the main reaction thing, n-Butyl Amine 99 and ammonium chloride grow the material of sheet and chrysanthemum shape during as promotor at alloy surface.

Claims

1, a kind of Mg-Li alloy surface organic matter method of reducing is characterized in that:

In the following order the Mg-Li alloy is carried out pre-treatment: carry out grinding process with sand paper, ultrasonic cleaning 15 minutes, distilled water flushing 30 seconds is used 50g/LNaOH+15g/LNaCO ₃+ 0.5g Sodium dodecylbenzene sulfonate carries out alkali cleaning, distilled water flushing 30 seconds, and the chromic anhydride solution acid pickling of 60g/L, washing dries up at last;

Organic reduction reaction

Adopt pickling process, reacting solution pH value is 6～7, and temperature of reaction is 60 ℃, and the main reaction thing is respectively aromatic hydrocarbons, ketone and carboxylic acid esters, and concrete reaction is for one of following:

(1), reactant is an aromatic hydrocarbons

Through early stage pretreated Mg-Li alloy put into fast in the reaction soln that the aromatic hydrocarbons reactant that prepared and promotor mixes and go, reactant is selected benzene or dimethylbenzene for use, the volume ratio of reactant, Virahol and ammonium chloride is 3: 3: 1, grows bar-shaped, needle-like and flap at alloy surface;

(2), reactant is a ketone

Premenstruum pretreated Mg-Li alloy put into apace in the mixing solutions of the ketone for preparing and promotor, the main reaction thing is selected methyl phenyl ketone for use, methyl phenyl ketone and aniline volume ratio are 4: 1, generate compact spheroidal particle at alloy surface;

(3), reactant is a carboxylic acid esters

Premenstruum, pretreated Mg-Li alloy will join in the mixing solutions that ester class and promotor forms fast, the main reaction thing is selected ethyl benzoate and ethyl acetate for use, n-Butyl Amine 99 and ammonium chloride grow the material of sheet and chrysanthemum shape during as promotor at alloy surface.