CN102079947A - Preparation method of titanium alloy surface sol-gel conversion film - Google Patents
Preparation method of titanium alloy surface sol-gel conversion film Download PDFInfo
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Abstract
The invention provides a preparation method of a titanium alloy surface sol-gel conversion film layer. In the sol-gel preparation method, the mixture of lower alcohol and water is taken as a solvent, organic siloxane and organic metal alkoxide which comprise organic functional groups are taken as precursors, organic acid is taken as a catalyst, dip coating is taken as a coating mode, and a prepared film layer can enhance the bonding force between a titanium alloy and an organic primer or a bonding agent. The mixture of the lower alcohol and water is taken as the solvent, so that problems of inflammability, safety, volatility and the like of a pure alcohol solvent and problems such as poor sol stability and short working life of a pure water solvent are solved. In the method, the mixture of the lower alcohol and water is taken as the solvent, so that the prepared sol can be kept clarified and transparent for a long time, and the film layer which is obtained by coating within at least one month is uniform and flat and has high bonding force.
Description
Technical field
The present invention relates to the technology of preparing of a kind of metallic surface conversion film, more particularly, at metallic substance be titanium alloy, the preparation method of conversion film adopts the sol-gel process of the mixture of rudimentary alcohol and water as solvent.
Background technology
Titanium alloy material is widely used in many industrial circles such as Aeronautics and Astronautics, building, automobile.In order to reach certain protection or function needs, for example solidity to corrosion, smooth finish, color and luster etc. need apply organic priming paint or binding agent at titanium alloy surface.And guarantee that organic priming paint or binding agent are key and the prerequisites that realizes that protection or function need with reliable, long-acting, firm the combining of titanium alloy surface.At present, the method that is used to strengthen organic priming paint or binding agent and titanium alloy surface bonding force generally is technology such as anodic oxidation.But a large amount of electric energy of anodizing technology consumption and water resources often contain the material of hostile environment such as a large amount of strong acid, highly basic and HUMAN HEALTH in the tank liquor, anodic oxidation simultaneously unavoidably can have a negative impact to the sample fatigue property.
The sol-gel conversion rete that sol-gel transforms rete technology, especially hybrid inorganic-organic is that present technical superiority is fairly obvious, the substitute technology that application prospect is very bright.Sol-gel transform rete can be respectively with metallic matrix and organic priming paint or binding agent with covalent bonds, solid and reliable, play the effect that connects metallic matrix and organic priming paint or binding agent.The raw material that sol-gel process adopts is to environment and body harmless, and consumed power does not need specific installation, and processes such as the preparation of colloidal sol and rete coating, drying are simple and easy to do, and maintenance maintenance is convenient.The method that sol-gel method adopts liquid colloidal sol to apply prepares rete, can obtain even, smooth film on the complex parts surface, can the mechanics or the fatigue property of metallic matrix not had a negative impact.What present research and development to this field sol-gel technique comparatively took the lead is Boeing Co., and the colloidal sol product that it is produced has dropped into commercial the use as PPG EAP-9, EAP-12 etc.
Be used to improve the sol-gel technique of metallic matrix and organic priming paint bonding force at present, employed solvent is a lower alcohol, as methyl alcohol, ethanol, Virahol etc., or deionized water.Solvent is as one of significant effects factor in the sol system, and its difference can produce tremendous influence to structure, the performance of final rete.The influence of solvent mainly is to realize by the degree that changes presoma hydrolysis, polycondensation.Common recognition is depicted as hydrolysis, the polycondensation equation of the silane that comprises three alkoxyl groups, and wherein R is that carbon atom is equal to or less than 5 alkyl; R ' is for containing or do not contain the carbochain of organic functions group, as epoxy group(ing), amino etc.
It with the lower alcohol system of solvent, be in the alcohol radical sol system, (the add-on of water≤5wt%) generally speaking, of the content by the water that added of control, can comparatively accurately control hydrolysis, polycondensation degree and the product structure of presoma, this is favourable to the rete that design meets the requirements.But the use of a large amount of alcohol can produce the problem of aspects such as inflammableness, security, needs to formulate very strict security control, storage safeguards in practical application in industry, and this has just increased the application risk and the cost of pure based sols.On the other hand, very strong as the pure volatility of solvent, especially true in the higher environment of temperature, this will change the concentration of sol system, and then the hydrolysis of presoma, polycondensation speed, degree etc. are produced unknowable influence.Therefore consider from the stable aspect of sol system that adopting alcohol also is inappropriate as solvent.
In order to evade the disadvantageous effect that alcoholic solvent produces, some investigators adopt water as solvent.But the water base sol system tends to produce within a short period of time precipitation, the suitable film forming time of coating is generally short (under the room temperature open environment, generally be no more than 24 hours working life), because sedimentary generation has changed the concentration of presoma material in the colloidal sol in fact, cause the stability of sol system to reduce.
Angle from molecular balance, the simple lower alcohol that adopts is as solvent, can suppress hydrolysis reaction, cause the hydrolysis of silane incomplete, the equilibrium state that can only acquire a certain degree, thereby the silanol groups-Si-OH in the colloidal sol is less, i.e. the reactant of polycondensation is less relatively, be unfavorable for the crosslinked and densification of rete, more be unfavorable for producing between rete and the metallic matrix enough chemical bonds and combine; The simple water as solvent that adopts, it is generally acknowledged the hydrolysis that silane can be completely or almost completely, though this can produce enough silanol groups-Si-OH, but be easy in the local excessive polymerization, thereby the precipitation of generation, change the precursor concentration in the colloidal sol in fact, also be unfavorable for the long storage and the use of colloidal sol.
Except solvent composition, sol system can be subjected to the influence of other several factors, for example temperature of reaction, stirring velocity etc.Generally speaking, temperature of reaction is high more, and the hydrolysis reaction equilibrium constant is big more, and the presoma hydrolysis is abundant more, and the silanol that is generated-Si-OH content is high more, helps combining of follow-up and metallic surface more; But temperature of reaction is high more simultaneously, and the also corresponding increase of the degree of polyreaction not only consumes part silanol groups-Si-OH, also can increase dissolved adhesiveness, the oligopolymer that is generated even can cause sedimentary a large amount of generation, this has just reduced the colloidal sol quality, shortens colloidal sol working life.Therefore, the temperature of reaction that the colloidal sol process for preparation rationally is set has considerable influence for the final effect of colloidal sol.
Stirring velocity in the colloidal sol process for preparation also has certain influence to sol system.The effect of stirring mainly is by mechanical force presoma to be dispersed in the solvent, and this point is particularly important in the process for preparation of colloidal sol.Because the polyreaction in the sol system generally all is to be core with the larger particles of having deposited in the colloidal sol, and then development grows up, and as not adding control, finally will form precipitation.The high purity presoma is being joined in the solvent, and in the mutual mixing process of dissimilar precursor sols, if stir insufficient, cause in the concentration of regional area presoma excessive possibly, (dehydration polymerization, dealcoholysis polymerization can take place in its polyreaction fast, or the two all takes place), produce relatively large polymkeric substance, and then become follow-up polymeric reaction core.Moreover, the polymkeric substance that has produced is general difficultly to be decomposed into small molecules by hydrolysis reaction again, so these are present in the polymkeric substance in the colloidal sol, as long as the ambient conditions maturation, just may cause polyreaction continue carry out, make the reduction of sol system stability.Comprehensive, stirring in the colloidal sol process for preparation is very crucial, must just presoma fully be disperseed in the mixing beginning, make it reach predetermined concentration immediately, and produce not concentrate in the part, this will rooting according to Rational Parameters selection stirring velocitys such as the viscosity of preparation material, solvability, reactive behavioies.
In sum, the present invention considers from the mechanism of sol gel reaction, the mixture that adopts rudimentary alcohol and water is a solvent, and carry out choose reasonable at factors such as the temperature of reaction in the colloidal sol layoutprocedure, stirring velocitys, when guaranteeing colloidal sol quality stable to greatest extent, prepared membrane has also obtained the bonding force between higher titanium alloy and organic priming paint or the binding agent.
Summary of the invention
The object of the present invention is to provide a kind of sol-gel that is used for titanium alloy surface to transform the preparation method of rete, this process for preparing sol-gel adopts the mixture of rudimentary alcohol and water to be solvent, to be presoma, to be catalyzer with the organic acid with organo-siloxane and the organo-metallic alkoxide that contains the organic functions group, coating method is dip-coating, and prepared membrane can improve bonding force between titanium alloy and organic priming paint or the binding agent.
Concrete technical process of the present invention comprises that mainly test button is handled, colloidal sol is prepared, rete applies, dry four parts of rete as shown in Figure 2, and the detailed technology scheme is as follows:
1) test button is handled
The pre-treatment of titanium alloy sample adopts the regulation in aircraft industry standard HB/Z 347-2002 " titanium or titanium alloy anode oxidation process " or the United States Patent (USP) 4,614,607 to carry out.
The surface that it should be noted that the titanium alloy sample is disposing, and will carry out must be able to keeping continuous moisture film more than 60 seconds, otherwise need handling to reach above-mentioned effect again before the colloidal sol coating.
2) colloidal sol preparation
The preparation of mixed solvent 1: prepare the mixture of rudimentary alcohol and water by a certain percentage, wherein lower alcohol comprises methyl alcohol, ethanol, Virahol, n-propyl alcohol etc., preferred alcohol; Water generally adopts deionized water; The volume ratio ratio of rudimentary alcohol and water is 20%-50%, preferred 30-35%;
The preparation of organo-siloxane colloidal sol 2: under certain temperature and magnetic agitation, organo-siloxane is slowly poured in the above-mentioned mixed solvent 1, and continued to stir about 1 hour, wherein certain temperature refers to 10-50 ℃, preferred 20-30 ℃; The magnetic agitation rotating speed is 500-1000rpm.Organo-siloxane is selected from γ-glycidyl ether oxygen propyl trimethoxy silicane, 3-glycidyl ether oxygen ylmethyl diethoxy silane, 2-(3,4-epoxy cyclohexane base) ethyl trimethoxy silane, 2-(3,4-epoxy cyclohexane base) ethyl triethoxysilane, γ-An Bingjisanyiyangjiguiwan, N-2-aminoethyl-3-aminopropyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane, 1, two (trimethoxy the is silica-based) ethane, 1 of 2-, two (triethoxy is silica-based) ethane of 2-or their mixture; The volume ratio of organo-siloxane is 2%-10%, preferred 5%-7%;
The preparation of organo-metallic alkoxide and organic acid mixture 3: under certain temperature and magnetic agitation situation, a certain amount of organo-metallic alkoxide and organic acid or other hydrolysis inhibitors are mixed, wherein certain temperature refers to 10-50 ℃, preferred 20-30 ℃; The magnetic agitation rotating speed is 500-1000rpm.The organo-metallic alkoxide of organo-metallic alkoxide selected among zirconium (Zr), cerium (Ce), titanium (Ti) or yttrium (Y), for example propyl alcohol zirconium, methoxy ethoxy yttrium, n-propyl alcohol yttrium, butanols titanium etc., preferably propyl alcohol zirconium; Organic acid or hydrolysis inhibitor are selected from acetate, oxalic acid, citric acid, methyl ethyl diketone etc., preferred acetate; Organo-metallic alkoxide and organic acid volume ratio ratio are 1～3: 1, preferred 2: 1;
Organo-metallic alkoxide and organic acid mixture are continued to stir 5-15 minute;
At rotating speed is under the violent stirring of 1200-1600rpm, above-mentioned metal alkoxide and organic acid mixture 3 are slowly joined in the above-mentioned organo-siloxane colloidal sol 2, at 10-30 ℃, the rotating speed of 500-1000rpm stirred 1-2 hour down, obtain required mixed sols, set aside for use, blending ratio should satisfy silane: the volume ratio of metal alkoxide is 1～4: 1, preferred 2: 1;
After mixed sols preparation was finished, it was stand-by to seal room temperature preservation.
3) rete applies
Adopt dip coating to prepare rete, dipping time is 30 seconds-10 minutes; Take-off speed is 1-10cm/min; Apply number of times as required, select 1-4 time; Sample is dry at ambient temperature 10-20 minute between each the coating, or adopts clean pressurized air to ease up and brushed surperficial 1-2 minute.
4) rete drying
At first at room temperature dry 10-20 minute of the sample that coating finishes, or adopt clean pressurized air to ease up and brushed surperficial 5-10 minute, in air, be heated to 40-120 ℃ then and solidified 10 minutes-4 hours, cool to room temperature then with the furnace, and under room temperature environment, preserve.
The invention has the advantages that:
The mixture that adopts rudimentary alcohol and water is as solvent, be different from and use alcohol in the prior art merely or use water as solvent merely, both overcome problems such as inflammableness that simple alcoholic solvent can produce, security, volatility, overcome again collosol stability difference that simple water solvent can produce and working life short problem.The mixture that adopts rudimentary alcohol and water of the present invention is as solvent, and the even film layer that prepared colloidal sol can keep clear for a long time and coating obtains in the time of at least one month is smooth, and bonding force is good.
Adopt sol-gel process of the present invention to transform rete, can improve the bonding force between titanium alloy and organic priming paint or the binding agent, with reference to ASTM D 3359-97Standard Tests at the even complete sol-gel of titanium alloy surface preparation
The related request of Methods for Measuring Adhesion by Tape Test, the bonding force that sol-gel of the present invention transforms between rete and metallic matrix and organic priming paint or the binding agent all can reach more than the 4B level; Compare with conventional anodization, consumed power does not contain poisonous objectionable impurities, can the mechanics or the fatigue property of metallic matrix not had a negative impact.
Colloidal sol of the present invention can be preserved for a long time, and the excellent film forming properties of maintenance, and the bonding force excellence of rete and metallic matrix and organic priming paint, but so just effectively prolonged the engineering time of sol-gel conversion film technology, save starting material, avoided short limitation working life that exists in the current sol-gel conversion film preparation effectively.Compare with the water base sol product E AP-9 of Boeing Co., colloidal sol of the present invention reached 1 month working life, much larger than 24 hours of EAP-9.
Shown in Figure 1 is to adopt the colloidal sol of formulation of the present invention to preserve the exterior appearance of 1 month prepared rete in front and back and draw the lattice pattern in the room temperature sealing, wherein Fig. 2 a, c were respectively the colloidal sol preservation 1 day and the outward appearance of 30 days prepared retes, and Fig. 2 b, d are respectively pairing stroke of lattice pattern of above-mentioned rete.Can see through the room temperature sealing metallic surface of having preserved the still evenly complete covering of 30 days colloidal sol prepared membrane, not having crackle from exterior appearance, film forming properties is good; From drawing the lattice pattern as can be seen, colloidal sol different prepared retes of shelf time to draw lattice pattern corner angle clearly demarcated, do not have obscission, all reached more than the 5B level according to the regulation of ASTM D 3359-97.
Description of drawings
Fig. 1 is a processing step schema of the present invention;
Fig. 2 is the exterior appearance of colloidal sol preservation different time coating sample and drew lattice pattern a, c-1 days; B, d-30 days;
Fig. 3 is that colloidal sol is placed 1 day sample rete section SEM photo among the embodiment 1;
Fig. 4 is that colloidal sol is placed 30 days sample rete section SEM photos among the embodiment 1;
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
Embodiment 1
1) titanium alloy sample pre-treatment
The pre-treatment of titanium alloy sample adopts the regulation in navigation mark HB/Z 347-2002 " titanium or titanium alloy anode oxidation process " or the United States Patent (USP) 4,614,607 to carry out.
2) colloidal sol preparation
At first 120ml dehydrated alcohol and 280ml deionized water are poured in the 500ml beaker, at room temperature stir (magnetic agitation rotating speed 500-1000rpm) obtains mixed solvent 1.28ml γ-glycidyl ether oxygen propyl trimethoxy silicane is slowly poured in the above-mentioned mixed solvent 1, and sealing stir about 45-60min, organo-siloxane colloidal sol 2 obtained.
Meanwhile, 7ml Glacial acetic acid and 14ml zirconium-n-propylate (75%) are poured in the 100ml beaker successively, the room temperature lower magnetic force stirs (rotating speed 500-1000rpm) about 30min, obtains organo-metallic alkoxide and organic acid mixture 3.
Under the vigorous stirring (rotating speed 1200-1600rpm), above-mentioned organo-metallic alkoxide and organic acid mixture 3 are poured in the above-mentioned organo-siloxane colloidal sol 2 slowly, after (rotating speed 500-1000rpm) 1h is stirred in sealing under the room temperature, obtained required colloidal sol, set aside for use.
3) the colloidal sol rete applies and is dry
The titanium alloy sample that pre-treatment is finished is immersed in the above-mentioned colloidal sol, keeps 5-10min, takes out with the speed of 10cm/min again.In the air at room temperature environment, sample is left standstill 10-15min, perhaps adopt clean pressurized air gentle brush specimen surface 1-2min.Repeat dip-coating twice, will leave standstill 10-15min under the sample chamber warm air environment then, place 60 ℃ the dry 1h of baking oven again, furnace cooling.
4) primer coating
The sample that coating finishes is deposited about 24h at first at ambient temperature, applies two component epoxy priming paint afterwards, and carries out corresponding solidification treatment.
Mixed sols according to above-mentioned steps preparation seals preservation at ambient temperature, and mixed sols can keep achromaticity and clarification transparent in one-month period at least, can not produce precipitation.Prepared membrane can even complete covering specimen surface, and has the good binding performance with matrix and priming paint.What table 1 showed is that above-mentioned mixed sols is placed the bonding force test result that different time applies sample.Fig. 2 is the profile scanning electromicroscopic photograph that prepared sol-gel transformed rete when colloidal sol was placed 1 day in the present embodiment.The specimen surface of therefrom can having seen covering that rete is complete, without any the phenomenon that comes off, thicknesses of layers is about about 1 μ m.Prepare that the cross-section morphology of rete is within the rule to be gone out 2-30 days storage period, its thicknesses of layers also remains in the above-mentioned scope, and storage period is of a specified duration more, and thicknesses of layers slightly increases, this may be since dissolved adhesiveness along with the time slightly raises.
The colloidal sol of table 1 embodiment 1 preparation prepares the bonding force of rete
* grade according to the regulation of ASTM D 3359-97
Embodiment 2
1) titanium alloy sample pre-treatment
The pre-treatment of titanium alloy sample adopts the regulation in navigation mark HB/Z 347-2002 " titanium or titanium alloy anode oxidation process " or the United States Patent (USP) 4,614,607 to carry out.
2) colloidal sol preparation
At first 80ml dehydrated alcohol and 320ml deionized water are poured in the 500ml beaker, at room temperature stir (magnetic agitation rotating speed 500-1000rpm) obtains mixed solvent 1.28ml γ-glycidyl ether oxygen propyl trimethoxy silicane is slowly poured in the above-mentioned mixed solvent 1, and sealing stir about 45-60min, organo-siloxane colloidal sol 2 obtained.
Meanwhile, 7ml Glacial acetic acid and 14ml zirconium-n-propylate (75%) are poured in the 100ml beaker successively, the room temperature lower magnetic force stirs (rotating speed 500-1000rpm) about 30min, obtains organo-metallic alkoxide and organic acid mixture 3.
Under the vigorous stirring (rotating speed 1200-1600rpm), above-mentioned organo-metallic alkoxide and organic acid mixture 3 are poured in the above-mentioned organo-siloxane colloidal sol 2 slowly, after (rotating speed 500-1000rpm) 1h is stirred in sealing under the room temperature, obtained required colloidal sol, set aside for use.
3) the colloidal sol rete applies and is dry
The titanium alloy sample that pre-treatment is finished is immersed in the mixed sols, keeps 5-10min, takes out with the speed of 10cm/min again.In the air at room temperature environment, sample is left standstill 10-15min, perhaps adopt clean pressurized air gentle brush specimen surface 1-2min.Repeat above-mentioned submergence-taking-up-air dried process 2 times, then sample is placed 60 ℃ the dry 0.5-1h of baking oven, furnace cooling.
4) primer coating
The sample that coating finishes need be in 72h primer coating, and solidification treatment.
Mixed sols according to the above-mentioned steps preparation seals preservation at ambient temperature, leaves standstill the basic clear that keeps in 15 days in the room temperature sealing, and no obvious sediment produces.After leaving standstill 15 days, begin to produce tiny visible particulate state precipitation, the colloidal sol transparency slightly descends.This phenomenon may be since in the solvent content of water big (80%) cause.Do not produce in the sedimentary time apply sample can even complete covering specimen surface, and have the good binding performance with matrix and priming paint.What table 2 showed is that above-mentioned mixed sols is placed the bonding force test result that different time applies sample.
The colloidal sol of table 2 embodiment 2 preparations prepares the bonding force of rete
*Regulation grading according to ASTM D 3359-97
Embodiment 3
1) titanium alloy sample pre-treatment
The pre-treatment of titanium alloy sample adopts the regulation in navigation mark HB/Z 347-2002 " titanium or titanium alloy anode oxidation process " or the United States Patent (USP) 4,614,607 to carry out.
2) colloidal sol preparation
At first 200ml dehydrated alcohol and 200ml deionized water are poured in the 500ml beaker, at room temperature stir (magnetic agitation rotating speed 500-1000rpm) obtains mixed solvent 1.28ml γ-glycidyl ether oxygen propyl trimethoxy silicane is slowly poured in the above-mentioned mixed solvent 1, and sealing stir about 45-60min, organo-siloxane colloidal sol 2 obtained.
Meanwhile, 7ml Glacial acetic acid and 14ml zirconium-n-propylate (75%) are poured in the 100ml beaker successively, the room temperature lower magnetic force stirs (rotating speed 500-1000rpm) about 30min, obtains organo-metallic alkoxide and organic acid mixture 3.
Under the vigorous stirring (rotating speed 1200-1600rpm), above-mentioned organo-metallic alkoxide and organic acid mixture 3 are poured in the above-mentioned organo-siloxane colloidal sol 2 slowly, after (rotating speed 500-1000rpm) 1h is stirred in sealing under the room temperature, obtained required colloidal sol, set aside for use.
3) the colloidal sol rete applies and is dry
The titanium alloy sample that pre-treatment is finished is immersed in the mixed sols, keeps 5-10min, takes out with the speed of 10cm/min again.In the air at room temperature environment, sample is left standstill 10-15min, perhaps adopt clean pressurized air gentle brush specimen surface 1-2min.Repeat above-mentioned submergence-taking-up-air dried process 2 times, then sample is placed 60 ℃ the dry 0.5-1h of baking oven, furnace cooling.
4) primer coating
The sample that coating finishes need be in 72h primer coating, and solidification treatment.
Mixed sols according to the above-mentioned steps preparation seals preservation at ambient temperature, and colloidal sol keeps achromaticity and clarification in originally 20 days, and no obvious sediment produces.After 20 days, the colloidal sol color begins to manifest light oyster white, and along with the time deepens gradually, the colloidal sol transparency descends gradually, but does not have obvious sediment to produce.After 1 month, have small quantities of particles shape precipitation to produce, colloidal sol still is creamy white, and is translucent, and viscosity rises to some extent.The generation of this phenomenon may be the ratio higher (50%) owing to alcohol in the solvent, makes that the colloidal sol volatilization is more, has promoted the polycondensation of siloxanes to a certain extent.What table 3 showed is that above-mentioned mixed sols is placed the bonding force test result that different time applies sample.Prepared membrane thickness and becomes big along with the time about 1 μ m, this be on the one hand since in the solvent content of alcohol bigger, cause mixed dissolved adhesiveness bigger; The concentration of silane is also bigger on the other hand, and it is big that the crosslinking degree of rete becomes.
The colloidal sol of table 3 embodiment 3 preparations prepares the bonding force of rete
* grade according to the regulation of ASTM D 3359-97
Claims (10)
1. a sol-gel that is used for titanium alloy surface transforms the preparation method of rete, the mixture that adopts rudimentary alcohol and water is solvent, is presoma, is catalyzer with the organic acid with organo-siloxane and the organo-metallic alkoxide that contains the organic functions group, it is characterized in that concrete steps are as follows:
1) test button is handled
The surface of titanium alloy sample is disposing, and will carry out keeping continuous moisture film more than 60 seconds before the colloidal sol coating;
2) colloidal sol preparation
The preparation of mixed solvent 1: prepare the mixture of rudimentary alcohol and water by a certain percentage, wherein lower alcohol is selected from methyl alcohol, ethanol, Virahol, n-propyl alcohol, and water generally adopts deionized water; The volume ratio ratio of rudimentary alcohol and water is 20%-50%;
The preparation of organo-siloxane colloidal sol 2: under certain temperature and magnetic agitation, organo-siloxane is slowly poured in the above-mentioned mixed solvent 1, and continued to stir about 1 hour, wherein certain temperature refers to 10-50 ℃, (write clump in addition and belong to claim); The magnetic agitation rotating speed is 500-1000rpm, organo-siloxane is selected from γ-glycidyl ether oxygen propyl trimethoxy silicane, 3-glycidyl ether oxygen ylmethyl diethoxy silane, 2-(3,4-epoxy cyclohexane base) ethyl trimethoxy silane, 2-(3,4-epoxy cyclohexane base) ethyl triethoxysilane, γ-An Bingjisanyiyangjiguiwan, N-2-aminoethyl-3-aminopropyl trimethoxysilane, 3-aminopropyl methyldiethoxysilane, 1, two (trimethoxy the is silica-based) ethane, 1 of 2-, two (triethoxy is silica-based) ethane of 2-or their mixture; The volume ratio content of organo-siloxane is 2%-10%;
The preparation of organo-metallic alkoxide and organic acid mixture 3: under certain temperature and magnetic agitation situation, a certain amount of organo-metallic alkoxide and organic acid or other hydrolysis inhibitors are mixed, wherein certain temperature refers to 10-50 ℃; The magnetic agitation rotating speed is 500-1000rpm, the organo-metallic alkoxide of organo-metallic alkoxide selected among zirconium (Zr), cerium (Ce), titanium (Ti) or yttrium (Y); Organic acid or hydrolysis inhibitor are selected from acetate, oxalic acid, citric acid, methyl ethyl diketone; Organo-metallic alkoxide and organic acid volume ratio ratio are 1～3: 1;
Organo-metallic alkoxide and organic acid mixture are continued to stir 5-15 minute;
At rotating speed is under the violent stirring of 1200-1600rpm, above-mentioned metal alkoxide and organic acid mixture 3 are slowly joined in the above-mentioned organo-siloxane colloidal sol 2, at 10-30 ℃, the rotating speed of 500-1000rpm keeps down stirring 1-2 hour, obtain required colloidal sol, set aside for use, blending ratio should satisfy silane: the volume ratio of metal alkoxide is 1～4, preferred 2: 1;
After the mixed sols preparation was finished, the sealing room temperature preservation was stand-by;
3) rete applies
Adopt dip coating to prepare rete, titanium alloy be impregnated in step 2) prepare in the colloidal sol, dipping time is 30 seconds-10 minutes; Take-off speed is 1-10cm/min; Apply number of times as required, select 1-4 time; Sample is dry at ambient temperature 10-20 minute between each the coating, or adopts clean pressurized air to ease up and brushed surperficial 1-2 minute;
4) rete drying
At first at room temperature dry 10-20 minute of the sample that coating finishes, or clean pressurized air is gentle brushed surperficial 5-10 minute, is heated to 40-120 ℃ then and solidified 10 minutes-4 hours in air, cools to room temperature then with the furnace, and preserves under room temperature environment.
2. preparation method as claimed in claim 1 is characterized in that: lower alcohol described in the solvent 1 is an ethanol;
3. preparation method as claimed in claim 1 is characterized in that: the volume ratio of rudimentary alcohol and water is 30-35% in the solvent 1;
4. colloidal sol preparation preparation method as claimed in claim 1, it is characterized in that: the preparation temperature of organo-siloxane colloidal sol 2, organo-metallic alkoxide and organic acid mixture 3 is 20-30 ℃;
5. preparation method as claimed in claim 1 is characterized in that: the organo-siloxane volume ratio in the organo-siloxane colloidal sol 2 is 5-7%;
6. preparation method as claimed in claim 1 is characterized in that: organo-metallic alkoxide and organic acid volume ratio are 2: 1 in organo-metallic alkoxide and the organic acid mixture 3;
7. preparation method as claimed in claim 1 is characterized in that: silane in the mixed colloidal sol: the volume ratio of metal alkoxide is 2: 1;
8. sol-gel as claimed in claim 1 transforms the preparation method of rete, and it is characterized in that: colloidal sol can be preserved for a long time, and colloidal sol reaches 1 month working life, and keeps excellent film forming properties.
9. sol-gel as claimed in claim 1 transforms the preparation method of rete, it is characterized in that: the sol-gel of preparation transforms rete, and is evenly complete; The bonding force that sol-gel transforms between rete and metallic matrix and organic priming paint or the binding agent can reach more than the 4B level.
10. sol-gel as claimed in claim 1 transforms the preparation method of rete, and it is characterized in that: the indication titanium alloy is TC4, TA15 and TC18.
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| CN102352184A (en) * | 2011-07-05 | 2012-02-15 | 温州市康尔微晶器皿有限公司 | Method for preparing sol for stabilizing properties of anti-reflection film of solar glass |
| CN103834301A (en) * | 2014-03-05 | 2014-06-04 | 西安钧盛新材料科技有限公司 | Preparation method of repairing material for scratches on self-focusing glass device |
| CN105419631A (en) * | 2015-12-21 | 2016-03-23 | 中国航空工业集团公司北京航空材料研究院 | Composite sol coating material for surface of aluminum alloy, and preparation method and coating method thereof |
| CN105463549A (en) * | 2015-12-03 | 2016-04-06 | 中国航空工业集团公司北京航空材料研究院 | Anodizing method improving protection performance of aluminum and aluminum alloy |
| CN106702457A (en) * | 2016-11-22 | 2017-05-24 | 西安理工大学 | Preparation method of zirconium oxide film for hole sealing of aluminium alloy plasma oxidation layer |
| CN110354303A (en) * | 2018-03-26 | 2019-10-22 | 北京化工大学 | A kind of antibacterial method of modifying of metallic titanium surface |
| CN113423512A (en) * | 2019-02-13 | 2021-09-21 | 凯密特尔有限责任公司 | Improved process for applying silane-based coatings to solid surfaces, particularly metal surfaces |
| CN114101002A (en) * | 2021-11-03 | 2022-03-01 | 哈尔滨飞机工业集团有限责任公司 | Surface treatment method before titanium alloy bonding |
| CN114618400A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Preparation method and application of cerium-zirconium sol |
| CN115279687A (en) * | 2020-02-12 | 2022-11-01 | 绿色溶胶-凝胶有限公司 | Sol application method |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352184B (en) * | 2011-07-05 | 2014-06-18 | 温州市康尔微晶器皿有限公司 | Method for preparing sol for stabilizing properties of anti-reflection film of solar glass |
| CN102352184A (en) * | 2011-07-05 | 2012-02-15 | 温州市康尔微晶器皿有限公司 | Method for preparing sol for stabilizing properties of anti-reflection film of solar glass |
| CN103834301A (en) * | 2014-03-05 | 2014-06-04 | 西安钧盛新材料科技有限公司 | Preparation method of repairing material for scratches on self-focusing glass device |
| CN103834301B (en) * | 2014-03-05 | 2016-08-24 | 西安钧盛新材料科技有限公司 | Self-focusing glass devices scratch removal material preparation method |
| CN105463549B (en) * | 2015-12-03 | 2018-06-26 | 中国航空工业集团公司北京航空材料研究院 | A kind of anodization process for improving aluminium and aluminium alloy barrier propterty |
| CN105463549A (en) * | 2015-12-03 | 2016-04-06 | 中国航空工业集团公司北京航空材料研究院 | Anodizing method improving protection performance of aluminum and aluminum alloy |
| CN105419631A (en) * | 2015-12-21 | 2016-03-23 | 中国航空工业集团公司北京航空材料研究院 | Composite sol coating material for surface of aluminum alloy, and preparation method and coating method thereof |
| CN106702457A (en) * | 2016-11-22 | 2017-05-24 | 西安理工大学 | Preparation method of zirconium oxide film for hole sealing of aluminium alloy plasma oxidation layer |
| CN106702457B (en) * | 2016-11-22 | 2018-11-06 | 西安理工大学 | A kind of preparation method of aluminium alloy plasma oxidation layer sealing of hole zirconia film |
| CN110354303A (en) * | 2018-03-26 | 2019-10-22 | 北京化工大学 | A kind of antibacterial method of modifying of metallic titanium surface |
| CN113423512A (en) * | 2019-02-13 | 2021-09-21 | 凯密特尔有限责任公司 | Improved process for applying silane-based coatings to solid surfaces, particularly metal surfaces |
| CN115279687A (en) * | 2020-02-12 | 2022-11-01 | 绿色溶胶-凝胶有限公司 | Sol application method |
| CN114618400A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Preparation method and application of cerium-zirconium sol |
| CN114101002A (en) * | 2021-11-03 | 2022-03-01 | 哈尔滨飞机工业集团有限责任公司 | Surface treatment method before titanium alloy bonding |
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