CN107815626A - A kind of almag making Nano surface technique - Google Patents
A kind of almag making Nano surface technique Download PDFInfo
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- CN107815626A CN107815626A CN201711066331.5A CN201711066331A CN107815626A CN 107815626 A CN107815626 A CN 107815626A CN 201711066331 A CN201711066331 A CN 201711066331A CN 107815626 A CN107815626 A CN 107815626A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/047—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with magnesium as the next major constituent
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
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Abstract
The invention discloses a kind of almag making Nano surface technique, comprise the following steps：The surface of almag is impacted with 12 18KHz frequency using power tungsten alloy cutter, enables to be strengthened so as to realize nanosizing by impact site.The almag making Nano surface technique of the present invention; after almag making Nano surface, surface modification treatment is carried out, hydrophobic, corrosion-resistant protective layer is formed on almag surface; waterproof, the anti-ice performance of almag are improved, there is good anti-wear performance and salt spray corrosion resistance.Be suitably applied member for automobile material, support, telescopic material such as article shading curtain, compared with traditional Steel material, not only component is light, also with good corrosion resistance, hardness is high, wearability is strong, good toughness the advantages of.
Description
Technical field
Present invention relates particularly to a kind of method for making Nano surface of almag.
Background technology
Almag has specific strength high, heat conduction and good conductivity, reflective be strong, in beautiful color, nonmagnetic, corrosion resistance
The advantages that good and plasticity and formability good, without black brittleness, be a kind of nonferrous materials with excellent comprehensive performance.Aluminium
Magnesium alloy has many advantages, such as, it is widely applied to various fields, and communications and transportation is mainly used in automobile, subway with almag
Vehicle, passenger train, the body construction part material of bullet train.But the chemical property of almag is active, in dry air
In its surface easily formed one layer of thin and compact oxide-film.And the case hardness of aluminium alloy it is low, it is resistance to one mill property it is poor, corrosion potential compared with
Negative, surface layer oxide film is easily corroded by strong acid and highly basic.Therefore the application of almag is limited to a certain extent.So exploitation
One kind has high intensity, corrosion resistant almag process of surface treatment very necessary.
Making Nano surface can make the surface of almag form nanostructured, the overall chemical component without changing material
And phase composition.Surface nanotechnology is combined with chemical treatment, chemical place is carried out to material after nanostructured surface laye is formed
Reason, different from basic chemical composition, fine and close, high anti-corrosion compound can be obtained on the top layer of material, is closed so as to improve magnesium
Gold surface corrosion resistance.The volume fraction increase for the crystal boundary that nanosizing is formed in material surface, interface can improve, and be the diffusion of atom
Preferable passage is provided, convenient condition is provided for the modification of almag.
The present invention forms protective layer to almag making Nano surface and chemical surface modification on almag surface,
Improve the hydrophobic of almag, anti-ice performance, anti-wear performance and salt spray corrosion resistance.Almag passes through making Nano surface
It is applied to member for automobile material, such as support, the telescopic material of article shading curtain after PROCESS FOR TREATMENT, compared with traditional Steel material,
Not only component is light, also with the advantages of anticorrosive property is good, hardness is high, wearability is strong, good toughness.
The content of the invention
The invention provides a kind of almag making Nano surface technique.The present invention adopts the following technical scheme that：
A kind of almag making Nano surface technique, comprises the following steps：
(1) size is impacted as 40mm × 20mm using 12-18KHz frequency using the tungsten alloy cutter that power is 280-480W
The surface of × 3mm almag, impact energy produce 450-650MPa compression；Enable by impact site strengthen so as to
Nanosizing is realized, nano-micrometre gradient-structure is formed on surface；
(2) almag after step (1) processing is put into quality as the almag quality 5-10 after step (1) processing
1-2min is soaked in machinery oil again, then does oil droplet.
A kind of almag making Nano surface technique, comprises the following steps：
(1) size is impacted as 40mm × 20mm using 12-18KHz frequency using the tungsten alloy cutter that power is 280-480W
The surface of × 3mm almag, impact energy produce 450-650MPa compression；Enable by impact site strengthen so as to
Nanosizing is realized, nano-micrometre gradient-structure is formed on surface；
(2) almag after step (1) processing is completely infused in quality as the almag matter after step (1) processing
Taken out in the metal hybrid Ludox of 5-10 times of amount after 15-30s, in 150-200 DEG C of dry 40-120min；The metal hybrid
Ludox is one kind in chromium hydridization Ludox, titanium hydridization Ludox, tin hydridization Ludox；
(3) almag after step (2) processing is put into quality as the almag quality 5-10 after step (2) processing
1-2min is soaked in machinery oil again, then does oil droplet.
A kind of almag making Nano surface technique, comprises the following steps, and described part is parts by weight：
(1) size is impacted as 40mm × 20mm using 12-18KHz frequency using the tungsten alloy cutter that power is 280-480W
The surface of × 3mm almag, impact energy produce 450-650MPa compression；Enable by impact site strengthen so as to
Nanosizing is realized, nano-micrometre gradient-structure is formed on surface；
(2) almag after step (1) processing is completely infused in quality as the almag matter after step (1) processing
Taken out in the metal hybrid Ludox of 5-10 times of amount after 15-30s, in 150-200 DEG C of dry 40-120min；The metal hybrid
Ludox is one kind in chromium hydridization Ludox, titanium hydridization Ludox, tin hydridization Ludox；
(3) 0.5-5 part cerous nitrates are added in 80-120 part water, under conditions of temperature is 20-40 DEG C, with 300-
500 revs/min of rotating speed stirring 30-60 minutes, 0.003-0.03 part organic acids are then added, are warming up to 1-5 DEG C/minute of speed
66-72 DEG C, 1-3 hours are stirred with 300-500 revs/min of rotating speed, obtain colloidal sol, the almag after step (2) processing is complete
In the colloidal sol of complete this step (3) for being immersed in 5-10 times of almag quality after quality is handled for step (2) after 15-30 minutes
Take out, after 420-480 DEG C of dry 20-40 minute, natural cooling；The organic acid is one in oxalic acid, citric acid, sulfamic acid
Kind or two or more mixtures.
(4) almag handled through step (3) is put into quality as the almag quality 5-10 after step (3) processing
1-2min is soaked in machinery oil again, then does oil droplet.
Preferably, the metal hybrid Ludox is chromium hydridization Ludox.
Preferably, the preparation method of the titanium hydridization Ludox is as follows, and described part is parts by weight：By the positive silicon of 50-80 parts
Sour methyl esters, 70-120 parts (3- aminopropyls) trimethoxy silane, 5-15 part isopropanols are added in 130-180 part ethanol, in temperature
Under conditions of 35-50 DEG C of degree, 1-3h is stirred with 300-800 revs/min of rotating speed, 2-6 parts acetic acid, 30-60 part water are added, in temperature
For 50-80 DEG C, 4-6h is stirred with 300-800 revs/min of rotating speed, adds 15-30 part metatitanic acids orthocarbonate, 50-100 part isopropanols,
It is 50-80 DEG C to continue in temperature, stirs 6-12 hours with 300-800 revs/min of rotating speed, obtains titanium hydridization Ludox.
Preferably, the preparation method of the chromium hydridization Ludox is as follows, and described part is parts by weight：By the positive silicon of 50-80 parts
Sour methyl esters, 70-120 parts (3- aminopropyls) trimethoxy silane, 5-15 part isopropanols are added in 130-180 part ethanol, in temperature
Under conditions of 35-50 DEG C of degree, 1-3h is stirred with 300-800 revs/min of rotating speed, 2-6 parts acetic acid, 30-60 part water are added, in temperature
For 50-80 DEG C, 4-6h is stirred with 300-800 revs/min of rotating speed, add double (trityl silylation) esters of 15-30 parts chromic acid,
50-100 part isopropanols, it is 50-80 DEG C to continue in temperature, stirs 6-12 hours with 300-800 revs/min of rotating speed, it is miscellaneous to obtain chromium
SiClx colloidal sol.
Preferably, the preparation method of the tin hydridization Ludox is as follows, and described part is parts by weight：By the positive silicon of 50-80 parts
Sour methyl esters, 70-120 parts (3- aminopropyls) trimethoxy silane, 5-15 part isopropanols are added in 130-180 part ethanol, in temperature
Under conditions of 35-50 DEG C of degree, 1-3h is stirred with 300-800 revs/min of rotating speed, 2-6 parts acetic acid, 30-60 part water are added, in temperature
For 50-80 DEG C, 4-6h is stirred with 300-800 revs/min of rotating speed, addition 15-30 part tributyl tin second cyanate, 50-100 parts are different
Propyl alcohol, it is 50-80 DEG C to continue in temperature, stirs 6-12 hours with 300-800 revs/min of rotating speed, obtains tin hydridization Ludox.
It is further preferred that the preparation method of the chromium hydridization Ludox is as follows, described part is parts by weight：By 50-80
Part methyl silicate, 70-120 parts (3- aminopropyls) trimethoxy silane, 5-15 part isopropanols are added to 130-180 part ethanol
In, under conditions of 35-50 DEG C of temperature, 1-3h is stirred with 300-800 revs/min of rotating speed, adds 2-6 parts acetic acid, 30-60 parts
Water, 0.01-0.1 part catalyst, it is 50-80 DEG C in temperature, 4-6h is stirred with 300-800 revs/min of rotating speed, adds 15-30 parts
Chromic acid double (trityl silylation) ester, 50-100 part isopropanols, it is 50-80 DEG C to continue in temperature, with 300-800 revs/min
Rotating speed stirs 6-12 hours, obtains chromium hydridization Ludox.
Preferably, the catalyst is one kind in phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid
It is further preferred that the catalyst is phosphomolybdic acid.
Preferably, the organic acid is that oxalic acid and sulfamic acid are (1-3) in mass ratio：The mixture of (1-2).
The almag making Nano surface technique of the present invention, after almag making Nano surface, carry out at the modification of surface
Reason, forms hydrophobic, corrosion-resistant protective layer on almag surface, improves waterproof, the anti-ice performance of almag, has good
Anti-wear performance and salt spray corrosion resistance.Member for automobile material is suitably applied, support, telescopic material such as article shading curtain,
Compared with traditional Steel material, not only component is light, also with good corrosion resistance, hardness is high, wearability is strong, good toughness the advantages of.
On the basis of common sense in the field is met, above-mentioned each optimum condition, it is each preferably can to produce the present invention in any combination
Embodiment.
Embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality
Apply among a scope.The experimental method of unreceipted actual conditions in the following example, conventionally and condition, or according to business
Product specification selects.
In following embodiments, primary raw material and instrument used are as follows：
Almag, purchased from Dongguan City Han Yong metal materials Co., Ltd, the trade mark 5052, chemical composition is shown in Table 1.
Table 1：5052 almag chemical component tables
| Element | Mg | Si | Fe | Cu | Mn | Cr | Zn | Al |
| Mass fraction | 2.3 | 0.052 | 0.27 | 0.066 | 0.072 | 0.17 | 0.070 | Surplus |
Methyl silicate, No. CAS：681-84-5, buy from Henan Tian Fu Chemical Co., Ltd.s.
(3- aminopropyls) trimethoxy silane, No. CAS：13822-56-5, buy from the limited public affairs of Nanjing chemical reagent share
Department.
Isopropanol, No. CAS：67-63-0, buy from Jiangsu Dong Yi Chemical Co., Ltd.s.
Ethanol, No. CAS：64-17-5, buy from Shandong departure Chemical Co., Ltd..
Acetic acid, No. CAS：64-19-7, buy from Henan Tian Fu Chemical Co., Ltd.s.
Double (trityl silylation) esters of chromic acid, No. CAS：1624-02-8, buy from Henan Tian Fu Chemical Co., Ltd.s.
Metatitanic acid orthocarbonate, No. CAS：3087-37-4, buy from Hangzhou great Yang Chemical Co., Ltd.s.
Tributyl tin second cyanate, No. CAS：681-99-2, buy from Tianjin Heowns Biochemical Technology Co., Ltd..
Phosphotungstic acid, No. CAS：12067-99-1, buy from Fuxin Yingkai Chemical Co., Ltd..
Phosphomolybdic acid, No. CAS：51429-74-4, buy from Nanjing Dao Sifu bio tech ltd.
Silico-tungstic acid, No. CAS：12027-38-2, buy from Henan Tian Fu Chemical Co., Ltd.s.
Cerous nitrate, No. CAS：10294-41-4, buy from the happy Chemical Co., Ltd.s of Jin Jin.
Oxalic acid, No. CAS：144-62-7, purchased from sincere hundred million Chemical Co., Ltd. in Nanjing.
Sulfamic acid, No. CAS：5329-14-6, purchased from Henan Tian Fu Chemical Co., Ltd.s.
Citric acid, No. CAS：77-92-9, purchased from Zhengzhou Brian Jacks Chemical Co., Ltd..
Machinery oil, the L-AN46# total loss of specifically used Shandong Bei Run petrochemical industry Co., Ltd production in the embodiment of the present invention
System oil.
In following embodiments, used test method and key instrument are as follows：
Water droplet contact angle is tested：With contact angle angular instrument (model DSA 100, producer：German Kruss) to through embodiment 1-
Almag after 7 almag making Nano surface PROCESS FOR TREATMENTs carries out surface water droplet contact angle test, environment temperature during test
Spend for 25 DEG C, water droplet dosage is 5.0 μ L, selects 10, almag product surface difference to be tested at random, test result takes 10
The average value of secondary result.
Salt spray corrosion resistance is tested：To embodiment 1, embodiment 2, embodiment 5-11 almag making Nano surface techniques
Almag after processing is sealed with paraffin, reserves 3cm × 5cm trial zone, and being placed in salt spray test chamber, (KD-60 types, purchase is certainly
Dongguan City Ke Di Instrument Ltd.) in carry out salt spray test.Corrosive liquid is the NaCl aqueous solution that mass fraction is 5%, experiment
Room θ be 35 DEG C, brine drum θ be 35 DEG C, pressure pot θ be 47 DEG C, in test process compressed air pressure be continuously held in (1.02 ±
0.01) bar, spraying sedimentation rate 80mL/ (cm2·h).Record almag trial zone starts the time corroded occur.
Anti-wear performance is tested：(bought using NM-1 types abrasion wear test machine from Jia, Shenzhen City Kodak Electronic Science and Technology Co., Ltd.)
Face coat wearability is carried out to the almag after embodiment 2, embodiment 5-11 almag making Nano surface PROCESS FOR TREATMENTs
It can be tested, experiment is friction head using scouring pad (Minnesota Mining and Manufacturing Company produces, model 7447), often rubs 100 times i.e. again
Change a scouring pad, be worn through with almag face coat the almag for exposing bottom when Rubbing number characterize magnalium
The wearability of alloy surface.
The present invention is further illustrated below by the mode of embodiment, unless otherwise specified, used number is attached most importance to
Measure number.
Embodiment 1
Almag making Nano surface technique, comprises the following steps：
(1) size is impacted as 40mm × 20mm × 3mm using 15KHz frequency using the tungsten alloy cutter that power is 480W
The surface of almag, impact energy produce 600MPa compression；Enable to be strengthened so as to realize nanosizing by impact site,
Nano-micrometre gradient-structure is formed on surface；
(2) almag after step (1) processing is put into quality as 10 times of almag quality after step (1) processing
Machinery oil in soak 2min, then oil droplet is done.
Embodiment 2
Almag making Nano surface technique, comprises the following steps：
(1) size is impacted as 40mm × 20mm × 3mm using 15KHz frequency using the tungsten alloy cutter that power is 480W
The surface of almag, impact energy produce 600MPa compression；Enable to be strengthened so as to realize nanosizing by impact site,
Nano-micrometre gradient-structure is formed on surface；
(2) almag after step (1) processing is completely infused in quality as the almag matter after step (1) processing
Taken out in the metal hybrid Ludox of 8 times of amount after 15s, in 180 DEG C of dry 40min；The metal hybrid Ludox is chromium hydridization
Ludox, the preparation method of the chromium hydridization Ludox are as follows：By 50 parts of methyl silicates, 70 parts of (3- aminopropyls) trimethoxies
Silane, 5 parts of isopropanols are added in 130 parts of ethanol, under conditions of 35 DEG C of temperature, are stirred 1h with 300 revs/min of rotating speed, are added
Enter 2 parts of acetic acid, 30 parts of water, be 50 DEG C in temperature, 4h is stirred with 300 revs/min of rotating speed, add the double (trityls of 15 parts of chromic acid
Silylation) ester, 50 parts of isopropanols, it is 50 DEG C to continue in temperature, is stirred 6 hours with 300 revs/min of rotating speed, obtains chromium hybrid silicon
Colloidal sol；
(3) almag after step (2) processing is put into quality as 10 times of almag quality after step (2) processing
Machinery oil in soak 2min, then oil droplet is done.
Embodiment 3
It is substantially the same manner as Example 2, differ only in：Metal hybrid Ludox described in the present embodiment 3 is titanium hybrid silicon
Colloidal sol.The preparation method of the titanium hydridization Ludox is as follows：By 50 parts of methyl silicates, 70 parts of (3- aminopropyls) trimethoxy silicon
Alkane, 5 parts of isopropanols are added in 130 parts of ethanol, under conditions of 35 DEG C of temperature, are stirred 1h with 300 revs/min of rotating speed, are added 2
Part acetic acid, 30 parts of water, it is 50 DEG C in temperature, 4h is stirred with 300 revs/min of rotating speed, adds 15 parts of metatitanic acid orthocarbonates, 50 parts of isopropyls
Alcohol, it is 50 DEG C to continue in temperature, is stirred 6 hours with 300 revs/min of rotating speed, obtains titanium hydridization Ludox.
Embodiment 4
It is substantially the same manner as Example 2, differ only in：Metal hybrid Ludox described in the present embodiment 3 is tin hybrid silicon
Colloidal sol.The preparation method of the tin hydridization Ludox is as follows：By 50 parts of methyl silicates, 70 parts of (3- aminopropyls) trimethoxy silicon
Alkane, 5 parts of isopropanols are added in 130 parts of ethanol, under conditions of 35 DEG C of temperature, are stirred 1h with 300 revs/min of rotating speed, are added 2
Part acetic acid, 30 parts of water, it is 50 DEG C in temperature, 4h is stirred with 300 revs/min of rotating speed, adds 15 parts of tributyl tin second cyanates, 50
Part isopropanol, it is 50 DEG C to continue in temperature, is stirred 6 hours with 300 revs/min of rotating speed, obtains tin hydridization Ludox.
Comparative example 1
Almag making Nano surface technique, comprises the following steps：
(1) size is impacted as 40mm × 20mm × 3mm using 15KHz frequency using the tungsten alloy cutter that power is 480W
The surface of almag, impact energy produce 600MPa compression；Enable to be strengthened so as to realize nanosizing by impact site,
Nano-micrometre gradient-structure is formed on surface；
(2) almag after step (1) processing is completely infused in quality as the almag matter after step (1) processing
Taken out in the Ludox of 8 times of amount after 15s, in 180 DEG C of dry 40min；The preparation method of the Ludox is as follows：By 50 parts of positive silicon
Sour methyl esters, 70 parts of (3- aminopropyls) trimethoxy silanes, 5 parts of isopropanols are added in 130 parts of ethanol, in 35 DEG C of condition of temperature
Under, 1h is stirred with 300 revs/min of rotating speed, adds 2 parts of acetic acid, 30 parts of water, is 50 DEG C in temperature, is stirred with 300 revs/min of rotating speed
4h is mixed, adds 50 parts of isopropanols, it is 50 DEG C to continue in temperature, is stirred 6 hours with 300 revs/min of rotating speed, obtains Ludox；
(3) almag after step (2) processing is put into quality as 10 times of almag quality after step (2) processing
Machinery oil in soak 2min, then oil droplet is done.
Embodiment 5
Almag making Nano surface technique, comprises the following steps：
(1) size is impacted as 40mm × 20mm × 3mm using 15KHz frequency using the tungsten alloy cutter that power is 480W
The surface of almag, impact energy produce 600MPa compression；Enable to be strengthened so as to realize nanosizing by impact site,
Nano-micrometre gradient-structure is formed on surface；
(2) almag after step (1) processing is completely infused in quality as the almag matter after step (1) processing
Taken out in the metal hybrid Ludox of 8 times of amount after 15s, in 180 DEG C of dry 40min；The metal hybrid Ludox is chromium hydridization
Ludox, the preparation method of the chromium hydridization Ludox are as follows：By 50 parts of methyl silicates, 70 parts of (3- aminopropyls) trimethoxies
Silane, 5 parts of isopropanols are added in 130 parts of ethanol, under conditions of 35 DEG C of temperature, are stirred 1h with 300 revs/min of rotating speed, are added
Enter 2 parts of acetic acid, 30 parts of water, 0.05 part of catalyst, be 50 DEG C in temperature, 4h is stirred with 300 revs/min of rotating speed, adds 15 parts of chromium
Sour double (trityl silylation) ester, 50 parts of isopropanols, it is 50 DEG C to continue in temperature, is stirred 6 hours with 300 revs/min of rotating speed,
Obtain chromium hydridization Ludox；The catalyst is phosphotungstic acid；
(3) almag after step (2) processing is put into machinery oil and soaks 2min, then do oil droplet.
Embodiment 6
It is substantially the same manner as Example 5, differ only in：Catalyst described in the present embodiment 6 is phosphomolybdic acid.
Embodiment 7
It is substantially the same manner as Example 5, differ only in：Catalyst described in the present embodiment 7 is silico-tungstic acid.
Embodiment 8
Almag making Nano surface technique, comprises the following steps：
(1) size is impacted as 40mm × 20mm × 3mm using 15KHz frequency using the tungsten alloy cutter that power is 480W
The surface of almag, impact energy produce 600MPa compression；Enable to be strengthened so as to realize nanosizing by impact site,
Nano-micrometre gradient-structure is formed on surface；
(2) almag after step (1) processing is completely infused in quality as the almag matter after step (1) processing
Taken out in the metal hybrid Ludox of 8 times of amount after 15s, in 180 DEG C of dry 40min；The metal hybrid Ludox is chromium hydridization
Ludox, the preparation method of the chromium hydridization Ludox are as follows：By 50 parts of methyl silicates, 70 parts of (3- aminopropyls) trimethoxies
Silane, 5 parts of isopropanols are added in 130 parts of ethanol, under conditions of 35 DEG C of temperature, are stirred 1h with 300 revs/min of rotating speed, are added
Enter 2 parts of acetic acid, 30 parts of water, 0.05 part of catalyst, be 50 DEG C in temperature, 4h is stirred with 300 revs/min of rotating speed, adds 15 parts of chromium
Sour double (trityl silylation) ester, 50 parts of isopropanols, it is 50 DEG C to continue in temperature, is stirred 6 hours with 300 revs/min of rotating speed,
Obtain chromium hydridization Ludox；The catalyst is phosphomolybdic acid；
(3) 2.8 parts of cerous nitrates are added in 80 parts of water, under conditions of temperature is 30 DEG C, with 300 revs/min of rotating speed
Stirring 30 minutes, 0.01 part of organic acid is then added, 66 DEG C are warming up to 2 DEG C/minute of speed, stirred with 300 revs/min of rotating speed
2 hours, colloidal sol is obtained, the almag after step (2) processing is completely infused in into quality closes for the magnalium after step (2) processing
Taken out in the colloidal sol of this step (3) of golden 8 times of amount after 15 minutes, after 420 DEG C are dried 20 minutes, natural cooling；It is described to have
Machine acid is oxalic acid.
(4) almag after step (3) processing is put into quality as 10 times of almag quality after step (3) processing
Machinery oil in soak 2min, then oil droplet is done.
Embodiment 9
Almag making Nano surface technique, comprises the following steps：
(1) size is impacted as 40mm × 20mm × 3mm using 15KHz frequency using the tungsten alloy cutter that power is 480W
The surface of almag, impact energy produce 600MPa compression；Enable to be strengthened so as to realize nanosizing by impact site,
Nano-micrometre gradient-structure is formed on surface；
(2) almag after step (1) processing is completely infused in quality as the almag matter after step (1) processing
Taken out in the metal hybrid Ludox of 8 times of amount after 15s, in 180 DEG C of dry 40min；The metal hybrid Ludox is chromium hydridization
Ludox, the preparation method of the chromium hydridization Ludox are as follows：By 50 parts of methyl silicates, 70 parts of (3- aminopropyls) trimethoxies
Silane, 5 parts of isopropanols are added in 130 parts of ethanol, under conditions of 35 DEG C of temperature, are stirred 1h with 300 revs/min of rotating speed, are added
Enter 2 parts of acetic acid, 30 parts of water, 0.05 part of catalyst, be 50 DEG C in temperature, 4h is stirred with 300 revs/min of rotating speed, adds 15 parts of chromium
Sour double (trityl silylation) ester, 50 parts of isopropanols, it is 50 DEG C to continue in temperature, is stirred 6 hours with 300 revs/min of rotating speed,
Obtain chromium hydridization Ludox；The catalyst is phosphomolybdic acid；
(3) 2.8 parts of cerous nitrates are added in 80 parts of water, under conditions of temperature is 30 DEG C, with 300 revs/min of rotating speed
Stirring 30 minutes, 0.01 part of organic acid is then added, 66 DEG C are warming up to 2 DEG C/minute of speed, stirred with 300 revs/min of rotating speed
2 hours, colloidal sol is obtained, the almag after step (2) processing is completely infused in into quality closes for the magnalium after step (2) processing
Taken out in the colloidal sol of this step (3) of golden 8 times of amount after 15 minutes, after 420 DEG C are dried 20 minutes, natural cooling；It is described to have
Machine acid is citric acid.
(4) almag after step (3) processing is put into quality as 10 times of almag quality after step (3) processing
Machinery oil in soak 2min, then oil droplet is done.
Embodiment 10
Almag making Nano surface technique, comprises the following steps：
(1) size is impacted as 40mm × 20mm × 3mm using 15KHz frequency using the tungsten alloy cutter that power is 480W
The surface of almag, impact energy produce 600MPa compression；Enable to be strengthened so as to realize nanosizing by impact site,
Nano-micrometre gradient-structure is formed on surface；
(2) almag after step (1) processing is completely infused in quality as the almag matter after step (1) processing
Taken out in the metal hybrid Ludox of 8 times of amount after 15s, in 180 DEG C of dry 40min；The metal hybrid Ludox is chromium hydridization
Ludox, the preparation method of the chromium hydridization Ludox are as follows：By 50 parts of methyl silicates, 70 parts of (3- aminopropyls) trimethoxies
Silane, 5 parts of isopropanols are added in 130 parts of ethanol, under conditions of 35 DEG C of temperature, are stirred 1h with 300 revs/min of rotating speed, are added
Enter 2 parts of acetic acid, 30 parts of water, 0.05 part of catalyst, be 50 DEG C in temperature, 4h is stirred with 300 revs/min of rotating speed, adds 15 parts of chromium
Sour double (trityl silylation) ester, 50 parts of isopropanols, it is 50 DEG C to continue in temperature, is stirred 6 hours with 300 revs/min of rotating speed,
Obtain chromium hydridization Ludox；The catalyst is phosphomolybdic acid；
(3) 2.8 parts of cerous nitrates are added in 80 parts of water, under conditions of temperature is 30 DEG C, with 300 revs/min of rotating speed
Stirring 30 minutes, 0.01 part of organic acid is then added, 66 DEG C are warming up to 2 DEG C/minute of speed, stirred with 300 revs/min of rotating speed
2 hours, colloidal sol is obtained, the almag after step (2) processing is completely infused in into quality closes for the magnalium after step (2) processing
Taken out in the colloidal sol of this step (3) of golden 8 times of amount after 15 minutes, after 420 DEG C are dried 20 minutes, natural cooling；It is described to have
Machine acid is sulfamic acid.
(4) almag after step (3) processing is put into quality as 10 times of almag quality after step (3) processing
Machinery oil in soak 2min, then oil droplet is done.
Embodiment 11
Almag making Nano surface technique, comprises the following steps：
(1) size is impacted as 40mm × 20mm × 3mm using 15KHz frequency using the tungsten alloy cutter that power is 480W
The surface of almag, impact energy produce 600MPa compression；Enable to be strengthened so as to realize nanosizing by impact site,
Nano-micrometre gradient-structure is formed on surface；
(2) almag after step (1) processing is completely infused in quality as the almag matter after step (1) processing
Taken out in the metal hybrid Ludox of 8 times of amount after 15s, in 180 DEG C of dry 40min；The metal hybrid Ludox is chromium hydridization
Ludox.The preparation method of the chromium hydridization Ludox is as follows：By 50 parts of methyl silicates, 70 parts of (3- aminopropyls) trimethoxies
Silane, 5 parts of isopropanols are added in 130 parts of ethanol, under conditions of 35 DEG C of temperature, are stirred 1h with 300 revs/min of rotating speed, are added
Enter 2 parts of acetic acid, 30 parts of water, 0.05 part of catalyst, be 50 DEG C in temperature, 4h is stirred with 300 revs/min of rotating speed, adds 15 parts of chromium
Sour double (trityl silylation) ester, 50 parts of isopropanols, it is 50 DEG C to continue in temperature, is stirred 6 hours with 300 revs/min of rotating speed,
Obtain chromium hydridization Ludox；The catalyst is phosphomolybdic acid；
(3) 2.8 parts of cerous nitrates are added in 80 parts of water, under conditions of temperature is 30 DEG C, with 300 revs/min of rotating speed
Stirring 30 minutes, 0.01 part of organic acid is then added, 66 DEG C are warming up to 2 DEG C/minute of speed, stirred with 300 revs/min of rotating speed
2 hours, colloidal sol is obtained, the almag after step (2) processing is completely infused in into quality closes for the magnalium after step (2) processing
Taken out in the colloidal sol of this step (3) of golden 8 times of amount after 15 minutes, after 420 DEG C are dried 20 minutes, natural cooling；It is described to have
Machine acid is that oxalic acid and sulfamic acid are 3 in mass ratio：2 mixture.
(4) almag after step (3) processing is put into quality as 10 times of almag quality after step (3) processing
Machinery oil in soak 2min, then oil droplet is done.
The test result of the present embodiment 10 is：Start the 142 days time corroded occur, anti-wear performance test result is 8500
It is secondary.
Effect example 1
Almag after almag making Nano surface PROCESS FOR TREATMENT of the present invention is subjected to surface water droplet contact angle test,
Test result is shown in Table 2.
Table 2：Water droplet contact angle test result table
| Contact angle (°) | |
| Embodiment 1 | 82 |
| Embodiment 2 | 153 |
| Embodiment 3 | 134 |
| Embodiment 4 | 141 |
| Embodiment 5 | 167 |
| Embodiment 6 | 172 |
| Embodiment 7 | 159 |
| Comparative example 1 | 128 |
The almag surface water droplet contact angle of embodiment 1 is less than 90 °, into hydrophily.Embodiment 2-4 is in embodiment 1
On the basis of almag is impregnated to chromium hydridization Ludox, titanium hydridization Ludox, tin hydridization Ludox, the Ludox of hydridization respectively
After drying almag surface formed containing chromium, titanium, tin protective layer, in hydrophobic structure, water droplet is in almag surface energy
It is enough to be condensed into the orbicule globule automatically, and can freely roll, prevent almag surface corrosion, freeze, also have necessarily
Automatically cleaning effect.Embodiment 5-7 has further been carried out preferably to the catalyst for preparing chromium hydridization Ludox, the catalysis effect of catalyst
Rate difference causes the structure of chromium hydridization Ludox different, therefore hydrophobic performance also differs.
Effect example 2
Almag after almag making Nano surface PROCESS FOR TREATMENT of the present invention is subjected to decay resistance test, test
It the results are shown in Table 3.
Table 3：Decay resistance test result table
Embodiment 5-7 impregnates chromium hydridization Ludox, the almag surface salt tolerant after drying process on almag surface
Mist corrosive nature improves.The protective layer that almag surface is formed effectively prevents salt fog to permeate.Embodiment 8-10 is being implemented
Continue the colloidal sol that one layer of cerous nitrate of dipping hydrolyzes to form on the basis of example 6 on surface, surface colloidal sol generates oxygen after high temperature drying
Change cerium, further increase decay resistance.
Effect example 3
Almag after almag making Nano surface PROCESS FOR TREATMENT of the present invention is subjected to wear-resisting energy test, test result
It is shown in Table 4.
Table 4：Anti-wear performance test result table
| Rubbing number (secondary) | |
| Embodiment 2 | 3500 |
| Embodiment 5 | 4000 |
| Embodiment 6 | 5500 |
| Embodiment 7 | 4500 |
| Embodiment 8 | 6500 |
| Embodiment 9 | 6000 |
| Embodiment 10 | 7000 |
| Embodiment 11 | 8500 |
| Comparative example 1 | 3000 |
The anti-wear performance of almag sealer is the important indicator for evaluating almag service life.Embodiment 8-
After 10 form cerium oxide protective layer on almag surface, the anti-wear performance and service life on almag surface are greatly enhanced,
During the inner tube for the vehicle shading curtain for being applied especially to need often to stretch, the frictional dissipation of non-woven fabrics and inner tube abrasion can be reduced.
Preferred embodiment of the invention described in detail above.It should be appreciated that one of ordinary skill in the art without
Creative work can is needed to make many modifications and variations according to the design of the present invention.Therefore, all technologies in the art
Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Technical scheme, all should be in the protection domain being defined in the patent claims.
Claims (8)
1. a kind of almag making Nano surface technique, it is characterised in that comprise the following steps：
(1) using the tungsten alloy cutter that power is 280-480W using 12-18KHz frequency impact size as 40mm × 20mm ×
The surface of 3mm almag, impact energy produce 450-650MPa compression；Enable to be strengthened so as to real by impact site
Existing nanosizing, nano-micrometre gradient-structure is formed on surface；
(2) almag after step (1) processing is put into quality as 5-10 times of almag quality after step (1) processing
1-2min is soaked in machinery oil, then does oil droplet.
2. a kind of almag making Nano surface technique, it is characterised in that comprise the following steps：
(1) using the tungsten alloy cutter that power is 280-480W using 12-18KHz frequency impact size as 40mm × 20mm ×
The surface of 3mm almag, impact energy produce 450-650MPa compression；Enable to be strengthened so as to real by impact site
Existing nanosizing, nano-micrometre gradient-structure is formed on surface；
(2) almag after step (1) processing is completely infused in quality as the almag quality 5- after step (1) processing
Taken out in 10 times of metal hybrid Ludox after 15-30s, in 150-200 DEG C of dry 40-120min；The metal hybrid silicon is molten
Glue is one kind in chromium hydridization Ludox, titanium hydridization Ludox, tin hydridization Ludox；
(3) almag after step (2) processing is put into quality as 5-10 times of almag quality after step (2) processing
1-2min is soaked in machinery oil, then does oil droplet.
3. a kind of almag making Nano surface technique, it is characterised in that comprise the following steps, described part is parts by weight：
(1) using the tungsten alloy cutter that power is 280-480W using 12-18KHz frequency impact size as 40mm × 20mm ×
The surface of 3mm almag, impact energy produce 450-650MPa compression；Enable to be strengthened so as to real by impact site
Existing nanosizing, nano-micrometre gradient-structure is formed on surface；
(2) almag after step (1) processing is completely infused in quality as the almag quality 5- after step (1) processing
Taken out in 10 times of metal hybrid Ludox after 15-30s, in 150-200 DEG C of dry 40-120min；The metal hybrid silicon is molten
Glue is one kind in chromium hydridization Ludox, titanium hydridization Ludox, tin hydridization Ludox；
(3) 0.5-5 part cerous nitrates are added in 80-120 part water, temperature be 20-40 DEG C under conditions of, with 300-500 turn/
The rotating speed stirring 30-60 minutes divided, 0.003-0.03 part organic acids are then added, 66-72 is warming up to 1-5 DEG C/minute of speed
DEG C, 1-3 hours are stirred with 300-500 revs/min of rotating speed, obtain colloidal sol, by the almag thorough impregnation after step (2) processing
Taken out in the colloidal sol of this step (3) that quality is 5-10 times of almag quality after step (2) processing after 15-30 minutes,
After 420-480 DEG C of dry 20-40 minute, natural cooling；The organic acid is oxalic acid, citric acid, it is a kind of in sulfamic acid or
Two or more mixtures.
(4) almag handled through step (3) is put into quality as 5-10 times of almag quality after step (3) processing
1-2min is soaked in machinery oil, then does oil droplet.
A kind of 4. almag making Nano surface technique as claimed in claim 2 or claim 3, it is characterised in that the titanium hybrid silicon
The preparation method of colloidal sol is as follows, and described part is parts by weight：By 50-80 parts methyl silicate, 70-120 parts (3- aminopropyls) three
Methoxy silane, 5-15 part isopropanols are added in 130-180 part ethanol, under conditions of 35-50 DEG C of temperature, with 300-800
Rev/min rotating speed stirring 1-3h, add 2-6 parts acetic acid, 30-60 part water, be 50-80 DEG C in temperature, with 300-800 revs/min
Rotating speed stirs 4-6h, adds 15-30 part metatitanic acids orthocarbonate, 50-100 part isopropanols, and it is 50-80 DEG C to continue in temperature, with 300-
800 revs/min of rotating speed stirring 6-12 hours, obtain titanium hydridization Ludox.
A kind of 5. almag making Nano surface technique as claimed in claim 2 or claim 3, it is characterised in that the chromium hybrid silicon
The preparation method of colloidal sol is as follows, and described part is parts by weight：By 50-80 parts methyl silicate, 70-120 parts (3- aminopropyls) three
Methoxy silane, 5-15 part isopropanols are added in 130-180 part ethanol, under conditions of 35-50 DEG C of temperature, with 300-800
Rev/min rotating speed stirring 1-3h, add 2-6 parts acetic acid, 30-60 part water, be 50-80 DEG C in temperature, with 300-800 revs/min
Rotating speed stirs 4-6h, adds 15-30 parts chromic acid double (trityl silylation) ester, 50-100 part isopropanols, continue be in temperature
50-80 DEG C, 6-12 hours are stirred with 300-800 revs/min of rotating speed, obtain chromium hydridization Ludox.
A kind of 6. almag making Nano surface technique as claimed in claim 2 or claim 3, it is characterised in that the tin hybrid silicon
The preparation method of colloidal sol is as follows, and described part is parts by weight：By 50-80 parts methyl silicate, 70-120 parts (3- aminopropyls) three
Methoxy silane, 5-15 part isopropanols are added in 130-180 part ethanol, under conditions of 35-50 DEG C of temperature, with 300-800
Rev/min rotating speed stirring 1-3h, add 2-6 parts acetic acid, 30-60 part water, be 50-80 DEG C in temperature, with 300-800 revs/min
Rotating speed stirs 4-6h, adds 15-30 part tributyl tin second cyanate, 50-100 part isopropanols, and it is 50-80 DEG C to continue in temperature,
6-12 hours are stirred with 300-800 revs/min of rotating speed, obtain tin hydridization Ludox.
A kind of 7. almag making Nano surface technique as claimed in claim 2 or claim 3, it is characterised in that the chromium hybrid silicon
The preparation method of colloidal sol is as follows, and described part is parts by weight：By 50-80 parts methyl silicate, 70-120 parts (3- aminopropyls) three
Methoxy silane, 5-15 part isopropanols are added in 130-180 part ethanol, under conditions of 35-50 DEG C of temperature, with 300-800
Rev/min rotating speed stirring 1-3h, add 2-6 parts acetic acid, 30-60 parts water, 0.01-0.1 part catalyst, be 50-80 DEG C in temperature,
4-6h is stirred with 300-800 revs/min of rotating speed, adds 15-30 parts chromic acid double (trityl silylation) ester, 50-100 part isopropyls
Alcohol, it is 50-80 DEG C to continue in temperature, stirs 6-12 hours with 300-800 revs/min of rotating speed, obtains chromium hydridization Ludox.
8. a kind of almag making Nano surface technique as claimed in claim 7, it is characterised in that the catalyst is phosphorus tungsten
One kind in acid, phosphomolybdic acid, silico-tungstic acid.
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Effective date of registration: 20190521 Address after: 226000 Dongba Formation of Zixing Village, Xingdong Town, Tongzhou District, Nantong City, Jiangsu Province Patentee after: Nantong Yuqi metal products Co. Ltd. Address before: No. 355, Xhenzhuang Town, Shanghai, Minhang District, Shanghai Patentee before: Shanghai HAN's Mould Shape Co., Ltd. |