A kind of anti-oxidant repair coating of the wide temperature range of carbonaceous material and repairing, preparation method
Technical field
The present invention relates to a kind of repair coating and method for repairing and mending, anti-oxidant more particularly to a kind of wide temperature range of carbonaceous material
Repair coating and method for repairing and mending.
Background technique
With carbon/carbon compound material, carbon/composite material of silicon carbide etc. for representative carbonaceous material with its excellent high-temperature mechanics
Performance, thermophysical property are widely used in multiple fields such as Aeronautics and Astronautics.
Carbonaceous material surface preparation antioxidant coating be realize its used for a long time in high temperature aerobic environment it is effective
Approach.Coating production is usually reaction sintering, chemical vapour deposition technique, plasma spraying method etc..Due to carbonaceous material
Substrate is softer, and in assembly, transport, use process, component surface coating forms holiday compared with cracky.Traditional coating system
Preparation Method is both needed to by pyroprocess, is difficult to carry out repairing to the product that has completed assembly and can not integrally carry out high-temperature process.
Currently, the research in terms of carbonaceous material patching coating discloses less, main research concentrates on the U.S. to space shuttle
The repairing technique of antioxidant coating, but technical detail not yet discloses.In the prior art, the method for repairing and mending of coating is still immature, repairs
The high-temperature stability of coating layer is poor, it is smaller to be applicable in temperature range, it is still necessary to which the feasibility for improving repair technology improves repair coating
Reliability expands the scope of application of repair coating.To solve the above problems, the present invention uses simple low temperature repair technology, it is real
Original position, the low temperature, Rapid-Repair of wide temperature range antioxidant coating are showed.
Summary of the invention
It is an object of the invention to overcome the above-mentioned deficiency of the prior art, a kind of anti-oxidant repair coating, the repairing are provided
Coating is well combined with matrix, has reliable wide temperature range antioxygenic property.
Another object of the present invention is to provide a kind of realization holiday original positions, low temperature, quick method for repairing and mending.
It is a further object of the present invention to provide a kind of low temperature of antioxidant coating, fast preparation method.
What above-mentioned purpose of the invention was mainly achieved by following technical solution: a kind of wide temperature range antioxygen of carbonaceous material
Change repair coating, form the material for repairing of the repair coating by following compound and mass percentage composition:
Binder 20%~40%,
Silicon 20%~50%,
Boron carbide 5%~20%,
Silicon carbide 0%~20%,
Diboron trioxide 0%~10%,
Dehydrated alcohol 5%~40%.
The binder is silica solution, phenolic resin or silicone resin.
The particle size range of the silicon, boron carbide and silicon carbide is 1 μm~50 μm, and purity is not less than 99%.
A kind of method for repairing and mending of the anti-oxidant repair coating of wide temperature range of carbonaceous material, steps are as follows:
(1) carbonaceous material local defect region is cleaned using dehydrated alcohol, judges whether the depth of fault location is big
In 1mm, if more than (2) are thened follow the steps;It is no to then follow the steps (3);
(2) according to binder 20%~40%, silicon 30%~50%, boron carbide 5%~10%, silicon carbide 10%~
20%, the proportion of dehydrated alcohol 5%~20% configures putty type material for repairing, carries out surface filling using knife coating, executes later
Step (3);
(3) according to binder 20%~30%, silicon 20%~40%, boron carbide 5%~20%, silicon carbide 0%~10%,
The proportion preparation material for repairing that solid concentration is low, viscosity is small of diboron trioxide 0%~10%, dehydrated alcohol 20%~40%, is adopted
Material for repairing is coated uniformly at carbonaceous material coating local defect with spread coating or spray coating method, covers defect and defect peripheral region
Domain guarantees that repair coating is uniform, smooth.
After step (3) processing completion and surface drying, rifle, quartz lamp or baking oven are dried using heat and realize adding for coating zone
Heat.
The maximum heating temperature of curing process is ± 10 DEG C of (120~200), and heating total time is 4h~10h.
A kind of preparation method of the wide temperature range antioxidant coating of carbonaceous material, steps are as follows:
(1) according to binder 20%~30%, silicon 20%~40%, boron carbide 5%~20%, silicon carbide 0%~10%,
The ratio range preparation antioxidant coating slurry of diboron trioxide 0%~10%, dehydrated alcohol 20%~40%;
(2) above-mentioned coating paste is coated uniformly on using spread coating or spray coating method by the object that need to carry out surface oxidation-resistant processing
Body surface face.
Handled in step (2) and complete and be heating and curing after surface drying, the maximum heating temperature of curing process be (120~
200) ± 10 DEG C, heating total time is 4h~10h.
50 μm~300 μm of coating layer thickness coated in the step (2).
The coating layer thickness of optimization is 100 μm~200 μm.
Compared with prior art, the present invention has the following advantages:
The present invention realize different substrate materials, the quick of carbonaceous material component surface antioxidant coating in different shaped face, low temperature,
Repairing in situ.
Silica solution, phenolic resin and silicone resin in repair coating of the present invention all have good caking property,
200 DEG C or less dry solidifications can be such that ceramic powder closely bonds, and it is compound to advantageously form the ceramic powder being well combined in matrix
Thin layer.The decomposition without organic matter, volatilization, the high-temperature oxidation resistance of repair coating are more steady under the high temperature conditions for silica sol binder
It is fixed;The caking property of phenolic resin and silicone resin is stronger, and solid phase residual rate is high under hot environment, the binding force of repair coating and substrate
It is more excellent, it is therefore desirable to which the higher putty type material for repairing of viscosity is generally using phenolic resin or silicone resin as binder.
Repair coating of the present invention is being actually used using the refractory ceramicses such as silicon, boron carbide, silicon carbide powder as filler
Hot environment in realize coating sintering reaction and surface Pyrex glaze levelling process.In the oxidation environment of middle low temperature region
Under, the diboron trioxide of original diboron trioxide and oxidation reaction production can form glass glazings in repair coating outer surface.
Under the oxidation environment of high-temperature-range, the silica of original silica and oxidation reaction formation can be in repair layer outer surface
Form glass glazings.Therefore, the repair coating can within the scope of wider temperature range (500 DEG C~1600 DEG C) formation Pyrex
Glaze layer realizes the antioxidant defense of carbonaceous material substrate.
The coating that material for repairing is uniform, smooth may be implemented in coating method of the present invention, fits to holiday type
Answering property is stronger, and coating thickness and number are relatively easy to control, and process implementing is simple, effective.
Heat of the present invention, which dries rifle, may be implemented repair layer heating, the solidification of smaller area, and general heat dries the outlet air of rifle
Temperature can reach 500 DEG C or more, can satisfy heating process requirement.Quartz lamp may be implemented large area repair layer heating,
Solidification can satisfy heating process requirement.
Carbon/carbon compound material repair coating of the present invention is examined in static oxidation environment under 800 DEG C, atmospheric environment
30min, coating is intact, matrix non-oxidation;30min is examined in static oxidation environment under 1100 DEG C, atmospheric environment, coating is complete
It is good, matrix non-oxidation;30min is examined in static oxidation environment under 1500 DEG C, atmospheric environment, coating is intact, matrix non-oxidation;
30min is examined in static oxidation environment under 1600 DEG C, atmospheric environment, coating is intact, matrix non-oxidation;In 1MW/m2Electric arc wind
600s is examined in the environment of hole, coating is intact, matrix non-oxidation.
Repair coating of the present invention and substrate binding force are relatively strong, surface hardness is higher.The carbon prepared using this method/
Carbon composite substrate repair layer bond quality (cross-hatching) is not less than 2 grades.
Detailed description of the invention
Fig. 1 is the preparation flow figure of the anti-oxidant repair coating of the wide temperature range of the present invention;
Specific embodiment
A kind of anti-oxidant repair coating of width temperature range, forming the repair coating includes high temperature resistant binder and filler.Institute
Stating high temperature resistant binder is silica solution, phenolic resin or silicone resin;The filler be silicon powder, boron carbide powder, carborundum powder and
Diboron trioxide etc., wherein the particle size range of the ceramic powders such as silicon powder, boron carbide powder and carborundum powder is 1 μm~50 μm, and purity is not
Less than 99%.
In above-mentioned repair coating, the mass percentage content of each component are as follows: silica solution, phenolic resin or silicone resin 20%
~40%, silicon 20%~50%, boron carbide 5%~20%, silicon carbide 0%~20%, diboron trioxide 0%~10% is anhydrous
Ethyl alcohol 5%~40%, the sum of described each group distribution ratio are 100%.Material proportion can be formulated according to the specific requirements of repairing area,
Slurry viscosity can be adjusted by binder and dehydrated alcohol content.The above material dispersion is mixed, borosilicate body is configured to
It is material for repairing.
As shown in Figure 1, being cleaned using dehydrated alcohol to carbonaceous material local defect region in mending course, then will
The material for repairing that the above method is prepared uniformly is brushed at carbonaceous material local defect, is handled differently with specific reference to the size of defect:
If the depth of fault location is greater than 1mm, such as blind hole, dell, groove, then the putty type repairing that solid concentration is high, viscosity is big is prepared
Material carries out surface filling using knife coating, then prepares the material for repairing that solid concentration is low, viscosity is small and (if being less than 1mm, directly adopt
Handled with the material for repairing), material for repairing is coated uniformly at carbonaceous material coating local defect using spread coating or spray coating method, is covered
Lid defect and defect peripheral region guarantee that repair coating is uniform, smooth.
The putty type material for repairing component and mass percent that above-mentioned solid phase content is high, viscosity is big are as follows:
Binder 20%~40%,
Silicon 30%~50%,
Boron carbide 5%~10%,
Silicon carbide 10%~20%,
Dehydrated alcohol 5%~20%.
The component and mass percent for the material for repairing that solid concentration is low, viscosity is small are as follows:
Binder 20%~30%,
Silicon 20%~40%,
Boron carbide 5%~20%,
Silicon carbide 0%~10%,
Diboron trioxide 0%~10%,
Dehydrated alcohol 20%~40%.
After surface drying, the heating that the heating tools such as rifle, quartz lamp, baking oven realize repairing area is dried using heat, curing process
Maximum heating temperature is 120 DEG C~200 DEG C, and heating total time is 4h~10h, is formed and the preferable ceramic powder of matrix bond quality
Compound thin layer completes the preparation of the anti-oxidant repair coating of wide temperature range.
In addition, for the field that can meet its antioxygenic property requirement, can directly using above-mentioned preparation solid concentration it is low,
The preparation method of the small material for repairing of viscosity carries out quick large area antioxidant coating preparation.The preparation and coating work of coating paste
Skill is same as above, and coating layer thickness is 50 μm~300 μm, and the coating layer thickness of optimization is 100 μm~200 μm, and curing mode can be with
It is carried out by the way of being heated in baking oven, completes the low temperature of antioxidant coating, quickly prepares.
With reference to the accompanying drawing and specific embodiment the present invention is described in further detail:
For the oxidation resistant carbon material of repairing to be coated, look first at its holiday, judge coating damage degree and
Range determines repair coating system and method for repairing and mending according to the sShape features and technical requirements on the product to be repaired surface.
Embodiment 1
The local coatings defects such as blind hole, dell, groove for the depth of fault location greater than 1mm, preparation solid concentration height,
The big putty type material for repairing of viscosity.Choose following material proportion: phenolic resin 20%, silicon 50%, boron carbide 5%, silicon carbide
20%, dehydrated alcohol 5%.Material for repairing is formed after the sufficient dispersion mixing of above-mentioned material.Material for repairing is coated using knife coating
To region to be repaired, carbonaceous material surface is filled.
Then, filling region surface is further brushed using viscosity lower slurry.Choose following material proportion: silicon is molten
Glue 30%, silicon 25%, boron carbide 20%, diboron trioxide 5%, dehydrated alcohol 20%.To the sufficient dispersion mixing of above-mentioned material
After form material for repairing.Material for repairing is coated to by region to be repaired using spread coating or spray coating method, applies repair coating and periphery original
Layer flushes.
After repair coating reaches predetermined thickness, first at room temperature surface drying 3h, then using quartz lamp to repairing area into
Row is heating and curing, and can use following curing process system:
100 ± 10 DEG C (heat preservations 2 ± 0.25h) are freely warming up to from room temperature, then be freely warming up to 150 ± 10 DEG C (keep the temperature 2 ±
0.25h), after being then freely warming up to 200 ± 10 DEG C (2 ± 0.25h of heat preservation), finally freely cool down.
Material for repairing is well-dried, after solidification, completes the preparation of repair coating.
To the sample for using embodiment 1 to carry out patching coating, in 1MW/m2600s is examined in arc tunnel environment, is only repaired
The surface layer of coating is lost, matrix non-oxidation.
Embodiment 2
The local coatings defects such as blind hole, dell, groove for the depth of fault location greater than 1mm, preparation solid concentration height,
The big putty type material for repairing of viscosity.Choose following material proportion: silicone resin 35%, silicon 35%, boron carbide 10%, silicon carbide
10%, dehydrated alcohol 10%.Material for repairing is formed after the sufficient dispersion mixing of above-mentioned material.Material for repairing is coated using knife coating
To region to be repaired, by blind hole, dell, groove filling-in.
Then, filling region surface is further brushed using viscosity lower slurry.Choose following material proportion: silicon tree
Rouge 20%, silicon 30%, boron carbide 5%, silicon carbide 5%, diboron trioxide 5%, dehydrated alcohol 35%.It is sufficient to above-mentioned material
Material for repairing is formed after dispersion mixing.Material for repairing is coated to by region to be repaired using spread coating or spray coating method, make repair coating with
Periphery original coating flushes.
After repair coating reaches predetermined thickness, first at room temperature surface drying 1h, then using heat dry rifle to repairing area into
Row is heating and curing, and can use following curing process system:
It is freely warming up to 80 ± 10 DEG C (1 ± 0.25h of heat preservation) since room temperature, then successively freely heats up three times, respectively
Reach 100 ± 10 DEG C of temperature (1 ± 0.25h of heat preservation), 120 ± 10 DEG C (1 ± 0.25h of heat preservation), 160 ± 10 DEG C (heat preservation 1 ±
0.25h), finally freely cool down.
Material for repairing is well-dried, after solidification, completes the preparation of repair coating.
To the sample for using embodiment 2 to carry out coating, 800 DEG C, 1100 DEG C, 1500 DEG C of static oxidation examination 10min are carried out,
Specimen surface coating is intact, and mend does not occur coating failure.
Embodiment 3
The local coatings defects such as blind hole, dell, groove for the depth of fault location greater than 1mm, preparation solid concentration height,
The big putty type material for repairing of viscosity.Choose following material proportion: silicone resin 25%, silicon 40%, boron carbide 5%, silicon carbide 15%,
Dehydrated alcohol 15%.Material for repairing is formed after the sufficient dispersion mixing of above-mentioned material.Combine the method brushed that will repair using blade coating
Feed supplement is coated to region to be repaired, by blind hole, dell, groove filling-in.
After completing repair coating coating, then first at room temperature surface drying 1h adds repairing area using quartz lamp
Heat cure can use following curing process system:
It is freely warming up to 100 ± 10 DEG C (2 ± 0.25h of heat preservation) since room temperature, then successively freely heats up twice, respectively
Reach 120 ± 10 DEG C of temperature (2 ± 0.25h of heat preservation), 160 ± 10 DEG C (2 ± 0.25h of heat preservation), finally freely cools down.
Material for repairing is well-dried, after solidification, completes the preparation of repair coating.
To the sample for using embodiment 3 to carry out coating, 1500 DEG C of static oxidation examination 30min, specimen surface coating are carried out
Intact, mend does not occur coating failure.
Embodiment 4
For the Large area coatings defect of no dell, groove etc., the slurry compared with low viscosity can be used.Choose following material
Proportion: silica solution 20%, silicon 35%, boron carbide 15%, diboron trioxide 2%, dehydrated alcohol 28%.It is sufficient to above-mentioned material
Material for repairing is formed after dispersion mixing.Material for repairing is coated to by region to be repaired using spread coating, coats number according to repair coating
Required thickness and every layer of thickness determines, generally requires repair coating and flushes with periphery original coating.
After repair coating reaches predetermined thickness, then first at room temperature surface drying 2h carries out repairing area using baking oven
It is heating and curing, following curing process system can be used:
It is freely warming up to 60 ± 10 DEG C (1 ± 0.25h of heat preservation) since room temperature, then successively freely heats up four times, respectively
Reach 80 ± 10 DEG C of temperature (1 ± 0.25h of heat preservation), 100 ± 10 DEG C (1 ± 0.25h of heat preservation), 120 ± 10 DEG C (heat preservation 1 ±
0.25h), 140 ± 10 DEG C (1 ± 0.25h of heat preservation), finally freely cool down.
Material for repairing is well-dried, after solidification, completes the preparation of repair coating.
To the sample for using embodiment 4 to carry out patching coating, in 1MW/m2600s is examined in arc tunnel environment, repairing applies
Layer does not fail, matrix non-oxidation.
Embodiment 5
For the carbonaceous material exemplar of wide temperature range antioxidant coating to be prepared, the coating paste compared with low viscosity can be used.
Choose following material proportion: phenolic resin 20%, silicon 25%, boron carbide 15%, dehydrated alcohol 40%.It is sufficient to above-mentioned material
Coating paste is formed after dispersion mixing.Coating paste is coated to by carbonaceous material sample surfaces using spread coating, coating time is several
Determine that overall thickness is about 150 μm according to thickness needed for repair coating and every layer of thickness.
After coating reaches predetermined thickness, then first at room temperature surface drying 1h is heating and curing to sample using baking oven,
Following curing process system can be used:
It is freely warming up to 60 ± 10 DEG C (2 ± 0.25h of heat preservation) since room temperature, then successively freely heats up twice, respectively
Reach 120 ± 10 DEG C of temperature (2 ± 0.25h of heat preservation), 180 ± 10 DEG C (2 ± 0.25h of heat preservation), finally freely cools down.
Sample is well-dried, after solidification, completes the preparation of repair coating.
To the sample for using embodiment 5 to carry out coating preparation, coating bond quality is 1 grade, carries out 1600 DEG C of static oxidations
30min is examined, specimen surface coating is intact, does not occur coating failure.
Unspecified part of the present invention belongs to common sense well known to those skilled in the art.