CN116042040B - Laser ablation engraving line sealant - Google Patents

Laser ablation engraving line sealant Download PDF

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Publication number
CN116042040B
CN116042040B CN202211706073.3A CN202211706073A CN116042040B CN 116042040 B CN116042040 B CN 116042040B CN 202211706073 A CN202211706073 A CN 202211706073A CN 116042040 B CN116042040 B CN 116042040B
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Prior art keywords
parts
laser ablation
mixed solvent
engraving line
resin
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CN116042040A (en
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王帅
张玲
杨魁
张誉严
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Yunnan Coal Chemical Application Technology Research Institute Co ltd
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Yunnan Coal Chemical Application Technology Research Institute Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/006Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/20Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films

Abstract

The invention provides a laser ablation engraving line sealant which is characterized by comprising the following components in parts by weight: 20-25 parts of SEPS resin, 5-10 parts of modified resin, 0.5-1 part of maleic anhydride, 0.2-0.5 part of initiator, 0.5-1 part of auxiliary cross-linking agent, 1-2 parts of antioxidant, 1-2 parts of drier and 64-72 parts of mixed solvent. The temporary sealing agent applied to the laser sintering etching molded lines of the chemical milling protective coating of the aerospace vehicle alloy material has the excellent corrosion resistance of 110 ℃ high temperature resistant, strong alkaline NaOH solution and normal temperature dilute nitric acid, has the characteristics of convenient coating and filling and short drying and film forming time, is tightly combined with a coating film of the chemical milling protective coating after drying and film forming, is not mutually dissolved, is easy to peel, and avoids the influence on the flatness of chemical milling lines caused by burrs and gaps in peeling of the sealing layer of the etched lines.

Description

Laser ablation engraving line sealant
Technical Field
The invention relates to a sealant for a metal material chemical milling protective coating engraving line, in particular to a laser ablation engraving line sealant, and belongs to the technical field of chemical milling protective coatings.
Technical Field
Chemical milling (hereinafter abbreviated as "milling") is a processing technique widely used in metal materials in the aerospace industry. According to different corrosive media, chemical milling is divided into acidification milling and alkalization milling, and protective paint is needed in chemical milling for protecting non-chemical milling parts from being corroded by chemical milling solution. With the improvement of chemical milling technology, in the multi-step chemical milling technology, a laser ablation method is adopted to finish one-step processing of all the etched lines, specifically: in the chemical milling process, according to the design requirement of a drawing, firstly stripping the protective coating of the area with the largest chemical milling depth, after chemical milling to the depth of the design requirement, sequentially stripping the protective coating of the subsequent area needing chemical milling, and finally completing the multi-step continuous chemical milling of the workpiece.
In the above processing technology, since all the etched lines are already processed by one-time ablation, before the chemical milling processing is performed, the etched lines which are not peeled off temporarily need to be sealed, otherwise, the metal at the etched line parts is exposed to the chemical milling solution and corroded. The traditional method is to fill the silicone sealant with alkali resistance at the position of the carved line, or to paint and fill the silicone sealant with acrylic ester in the position of the carved line, but the following defects which are difficult to overcome are all existed: the curing time of the silicone sealant is usually more than 24 hours, which is not beneficial to the continuity of production, and the bonding force between the cured silicone sealant and a metal material is too high, so that the cured silicone sealant is difficult to completely peel off when the cured silicone sealant needs to be peeled off, and residues are left, and the residual silicone sealant can cause incomplete chemical milling lines and easily cause defects such as break points, plaques and the like; the benzene solution of acrylic ester is relatively fast in drying speed, but the dried coating is brittle and hard, when the chemical milling protective coating film at the edge of the etched line is stripped, the acrylic ester sealing coating can be sawtoothed broken, so that the chemical milling line is sawtoothed, and meanwhile, the benzene solvent can be immersed into the chemical milling protective coating at the edge of the etched line, so that the bonding force of the edge of the chemical milling protective coating is uneven, and further the milling ratio parameter is influenced.
Disclosure of Invention
The invention aims to provide a sealant for sealing the carved line, namely: when the laser ablation engraving line is adopted in the chemical milling processing of the aerospace vehicle shell alloy material, the laser ablation engraving line is sealed and protected by the sealant provided by the invention, and the sealant has excellent strong acid and alkali corrosion resistance, has good binding force with metal materials such as aluminum alloy and titanium alloy, and is easy to peel off integrally.
The invention is completed by the following technical scheme: the laser ablation engraving line sealant is characterized by comprising the following components in parts by weight:
20-25 parts of SEPS resin
5-10 parts of modified resin
Maleic anhydride 0.5-1 parts
Initiator 0.2-0.5 part
0.5-1 part of auxiliary cross-linking agent
Antioxidant 1-2 parts
1-2 parts of drier
64-72 parts of mixed solvent.
The content of diblock in the molecular chain of the SEPS (styrene-ethylene/propylene-styrene block copolymer) is less than or equal to 1 percent.
The modified resin is one or two of rosin pentaerythritol ester and terpene phenolic resin, and the proportion of the two is arbitrary.
The initiator is dicumyl peroxide, and maleic anhydride and an SEPS molecular chain are grafted through the dicumyl peroxide.
The auxiliary cross-linking agent is one or two of trimethylolpropane trimethacrylate and triallyl isocyanurate, and the proportion of the two is arbitrary.
The antioxidant is as follows: 2-acrylic acid-2- (1, 1-dimethylethyl) -6- [ [3- (1, 1-dimethylethyl) -2-hydroxy-5-methylphenyl ] methyl ] -4-tolyl ester, 2, 6-di-tert-butyl-p-cresol, and the ratio of the two is arbitrary.
The drier is one or two of copper naphthenate and potassium 2-ethylhexanoate, and the proportion of the two is arbitrary.
The mixed solvent comprises the following components in percentage by mass: cyclohexane petroleum ether, acetone=3:2:1.
The invention provides a laser ablation engraving line sealant, which is prepared through the following process steps:
A. the preparation method comprises the following steps of:
20-25 parts of SEPS resin
5-10 parts of modified resin
Maleic anhydride 0.5-1 parts
Initiator 0.2-0.5 part
0.5-1 part of auxiliary cross-linking agent
Antioxidant 1-2 parts
1-2 parts of drier
64-72 parts of mixed solvent;
B. and B, preparing the raw materials prepared in the step A: adding SEPS, modified resin, maleic anhydride, an initiator, a crosslinking aid and an antioxidant into a high-speed stirrer, uniformly mixing to obtain a mixture, adding the mixture into a double-screw extruder, carrying out melt extrusion reaction, controlling the extrusion reaction temperature to be 100-130 ℃ and the extrusion screw rotating speed to be 300-600r/min to obtain extruded particles, and then drying for 5 hours at 80-100 ℃ for later use;
C. adding 80-90 wt% of the mixed solvent prepared in the step A into a reaction kettle, adding the extruded particles obtained in the step B in the stirring process, and continuously stirring until all materials are completely dissolved to obtain a dissolved material I;
D. adding 10-20wt% of the mixed solvent prepared in the step A into the drier prepared in the step A, so that the drier is completely dissolved in the mixed solvent to obtain a dissolution material II;
E. and C, adding the dissolution material I in the step C and the dissolution material II in the step D into the same reaction kettle, stirring and dispersing until uniform, and filtering to obtain the laser sintering etching type line sealant.
In the extrusion process of the step B, under the heating condition of 100-130 ℃, an initiator, namely dicumyl peroxide is decomposed to generate free radicals, so that maleic anhydride and a molecular chain of SEPS resin are subjected to grafting reaction, under the action of trimethylol propane trimethyl acrylate and triallyl isocyanurate modified cross-linking agent, the grafted SEPS-g-MAH is further connected with rosin pentaerythritol resin and terpene phenolic resin molecules of the modified resin to form a reticular structure, and therefore, the high-elasticity SEPS, the brittle rosin pentaerythritol resin and the terpene phenolic resin are subjected to linking reaction to form a whole, so that the material has more excellent corrosion resistance, and meanwhile, the physical properties such as tensile strength, elongation at break and the like are not reduced, and the binding force of the material and metal is greatly improved.
The sealant provided by the invention adopts a quick-drying mixed solvent, can be dried to form a film in a short time after being coated, does not erode a chemical milling protective coating on the edge of an engraving line, has higher strong alkali and strong acid corrosion resistance and better elasticity after being coated, and particularly grafts maleic anhydride and a SEPS molecular chain through an initiator, namely dicumyl peroxide, and further combines brittle and hard resin with excellent corrosion resistance and strong binding force with a flexible SEPS molecular chain under the action of a crosslinking aid, thereby obtaining a sealant material which has moderate binding force with an alloy material, moderate flexibility, good acid and alkali corrosion resistance and easy stripping, so that the alloy material on the position of the engraving line is not contacted with the chemical milling solution and corroded before being stripped, and can be completely separated from the protective coating when being stripped, thereby fundamentally solving the sealing technical problem of laser ablation engraving line in a multi-step milling disposable engraving process.
Detailed Description
The invention is further described in connection with the following examples which are given solely for the purpose of illustration and are not intended to limit the scope of the invention.
Example 1
1. The preparation method comprises the following steps of: 20 parts of SEPS resin (the content of diblock in a molecular chain is less than or equal to 1%), 10 parts of terpene phenolic resin, 0.5 part of maleic anhydride, 0.5 part of dicumyl peroxide, 0.5 part of trimethylolpropane trimethacrylate, 0.5 part of triallyl isocyanurate, 1 part of 2-acrylic acid-2- (1, 1-dimethyl ethyl) -6- [ [3- (1, 1-dimethyl ethyl) -2-hydroxy-5-methylphenyl ] methyl ] -4-methyl phenyl ester, 2 parts of copper naphthenate and 65 parts of mixed solvent;
2. adding SEPS resin, terpene phenolic resin, maleic anhydride, dicumyl peroxide, trimethylolpropane trimethacrylate, triallyl isocyanurate and 2-acrylic acid-2- (1, 1-dimethylethyl) -6- [ [3- (1, 1-dimethylethyl) -2-hydroxy-5-methylphenyl ] methyl ] -4-methyl phenyl ester into a stirrer, uniformly mixing to obtain a mixture, adding the mixture into a double-screw extruder, carrying out melt extrusion reaction, controlling the extrusion reaction temperature of the double-screw extruder to be 110 ℃ and the extrusion screw rotating speed to be 400r/min, and obtaining extruded granules;
3. adding 55 parts of the mixed solvent in the step 1 into a stirring reaction kettle, adding the extruded granule in the step 2 in the stirring process, and continuously stirring until all materials are completely dissolved into uniform colloid to obtain a dissolved material I;
4. adding 10 parts of the mixed solvent in the step 1 into 2 parts of copper naphthenate in the step 1, so that the copper naphthenate is completely dissolved in the mixed solvent to obtain a dissolution material II;
5. and (3) adding the dissolution material I in the step (3) and the dissolution material II in the step (4) into the same reaction kettle, stirring for more than 20 minutes, uniformly dispersing the dissolution material I and the dissolution material II, and filtering to obtain the laser sintering etching type linear sealant.
The laser ablation engraving line sealant has a total solid content of 35% and a viscosity of 40s.
And uniformly coating the prepared laser-etched molded line sealant on a multi-step chemical milling laser ablation line, naturally drying for 4 hours at normal temperature, and then putting the molded line sealant into chemical milling.
The performance test results of the obtained laser-etched molded line sealant are as follows:
drying time: the actual drying condition of the coating is tested by adopting a filter pressing method, and qualitative filter paper can fall freely;
alkali resistance: immersing the coating test piece in 250g/L NaOH solution, immersing for 8 hours at 110 ℃, and completely stripping the coating once without foaming or leakage and residue;
acid resistance: immersing the coated test piece into HNO with the mass concentration of 20% 3 Soaking in the solution for 6 hours, the coating is free from foaming and leakage, and the coating is completely peeled at one time without residue.
Example 2
1. The preparation method comprises the following steps of: 25 parts of SEPS resin (the content of diblock in a molecular chain is less than or equal to 1%), 5 parts of rosin pentaerythritol ester, 1 part of maleic anhydride, 0.2 part of dicumyl peroxide, 1 part of triallyl isocyanurate, 2 parts of 2, 6-di-tert-butyl-p-cresol, 1 part of potassium 2-ethylhexanoate and 65 parts of mixed solvent;
2. adding SEPS resin, rosin pentaerythritol ester, maleic anhydride, dicumyl peroxide, triallyl isocyanurate and 2, 6-di-tert-butyl-p-cresol into a stirrer to be uniformly mixed to obtain a mixture, adding the mixture into a double-screw extruder to perform melt extrusion reaction, and controlling the extrusion reaction temperature of the double-screw extruder to be 120 ℃ and the extrusion screw speed to be 300r/min to obtain extruded particles;
3. adding 60 parts of the mixed solvent in the step 1 into a stirring reaction kettle, adding the extruded granule in the step 2 in the stirring process, and continuously stirring until all materials are completely dissolved into uniform colloid to obtain a dissolved material I;
4. adding 5 parts of the mixed solvent in the step 1 into 1 part of the potassium 2-ethylhexanoate in the step 1, so that the potassium 2-ethylhexanoate is completely dissolved in the mixed solvent to obtain a dissolution material II;
5. and (3) adding the dissolution material I in the step (3) and the dissolution material II in the step (4) into the same reaction kettle, stirring for more than 20 minutes, uniformly dispersing the dissolution material I and the dissolution material II, and filtering to obtain the laser sintering etching type linear sealant.
The total solid content of the laser ablation engraving line sealant is 35 percent, and the viscosity is 60 seconds.
And uniformly coating the prepared laser-etched molded line sealant on a multi-step chemical milling laser ablation line, naturally drying for 4 hours at normal temperature, and then putting the molded line sealant into chemical milling.
The performance test results of the obtained laser-etched molded line sealant are as follows:
drying time: the actual drying condition of the coating is tested by adopting a filter pressing method, and qualitative filter paper can fall freely;
alkali resistance: immersing the coating test piece in 250g/L NaOH solution, immersing for 8 hours at 110 ℃, and completely stripping the coating once without foaming or leakage and residue;
acid resistance: immersing the coated test piece into HNO with the mass concentration of 20% 3 Soaking in the solution for 6 hours, the coating is free from foaming and leakage, and the coating is completely peeled at one time without residue.
Example 3
1. The preparation method comprises the following steps of: 22 parts of SEPS resin (the content of diblock in a molecular chain is less than or equal to 1%), 5 parts of rosin pentaerythritol ester, 5 parts of terpene phenolic resin, 0.8 part of maleic anhydride, 0.3 part of dicumyl peroxide, 0.5 part of trimethylolpropane trimethacrylate, 0.5 part of triallyl isocyanurate, 1 part of 2- (1, 1-dimethyl ethyl) -6- [ [3- (1, 1-dimethyl ethyl) -2-hydroxy-5-methylphenyl ] methyl ] -4-tolyl ester, 1 part of 2, 6-di-tert-butyl p-cresol, 1 part of copper naphthenate, 1 part of 2-potassium ethylhexanoate and 70 parts of mixed solvent;
2. adding SEPS resin, rosin pentaerythritol ester, terpene phenolic resin, maleic anhydride, dicumyl peroxide, trimethylolpropane trimethacrylate, triallyl isocyanurate, 2-acrylic acid-2- (1, 1-dimethylethyl) -6- [ [3- (1, 1-dimethylethyl) -2-hydroxy-5-methylphenyl ] methyl ] -4-tolyl ester and 2, 6-di-tert-butyl-p-cresol into a stirrer to uniformly mix, obtaining a mixture, adding the mixture into a double-screw extruder, carrying out melt extrusion reaction, controlling the extrusion reaction temperature of the double-screw extruder to be 130 ℃ and the extrusion screw speed to be 600r/min, and obtaining extruded granules;
3. adding 60 parts of the mixed solvent in the step 1 into a stirring reaction kettle, adding the extruded granule in the step 2 in the stirring process, and continuously stirring until all materials are completely dissolved into uniform colloid to obtain a dissolved material I;
4. adding 10 parts of the mixed solvent in the step 1 into 1 part of copper naphthenate and 1 part of potassium 2-ethylhexanoate in the step 1, so that the drier is completely dissolved in the mixed solvent to obtain a dissolution material II;
5. and (3) adding the dissolution material I in the step (3) and the dissolution material II in the step (4) into the same reaction kettle, stirring for more than 20 minutes, uniformly dispersing the dissolution material I and the dissolution material II, and filtering to obtain the laser sintering etching type linear sealant.
The laser ablation engraving line sealant has a total solid content of 30% and a viscosity of 30s.
And uniformly coating the prepared laser-etched molded line sealant on a multi-step chemical milling laser ablation line, naturally drying for 4 hours at normal temperature, and then putting the molded line sealant into chemical milling.
The performance test results of the obtained laser-etched molded line sealant are as follows:
drying time: the actual drying condition of the coating is tested by adopting a filter pressing method, and qualitative filter paper can fall freely;
alkali resistance: immersing the coating test piece in 250g/L NaOH solution, immersing for 8 hours at 110 ℃, and completely stripping the coating once without foaming or leakage and residue;
acid resistance: immersing the coated test piece into HNO with the mass concentration of 20% 3 Soaking in the solution for 6 hours, the coating is free from foaming and leakage, and the coating is completely peeled at one time without residue.

Claims (5)

1. The laser ablation engraving line sealant is characterized by comprising the following components in parts by weight:
20-25 parts of SEPS resin
5-10 parts of modified resin
Maleic anhydride 0.5-1 parts
Initiator 0.2-0.5 part
0.5-1 part of auxiliary cross-linking agent
Antioxidant 1-2 parts
1-2 parts of drier
64-72 parts of mixed solvent;
the preparation method comprises the following steps:
A. preparing materials according to the mass parts;
B. and B, preparing the raw materials prepared in the step A: adding SEPS resin, modified resin, maleic anhydride, an initiator, a crosslinking aid and an antioxidant into a high-speed stirrer, uniformly mixing to obtain a mixture, adding the mixture into a double-screw extruder, carrying out melt extrusion reaction, controlling the extrusion reaction temperature to be 100-130 ℃ and the extrusion screw rotating speed to be 300-600r/min, and obtaining extrusion granules;
C. adding 80-90 wt% of the mixed solvent prepared in the step A into a reaction kettle, adding the extruded particles obtained in the step B in the stirring process, and continuously stirring until all materials are completely dissolved to obtain a dissolved material I;
D. adding 10-20wt% of the mixed solvent prepared in the step A into the drier prepared in the step A, so that the drier is completely dissolved in the mixed solvent to obtain a dissolution material II;
E. adding the dissolution material I in the step C and the dissolution material II in the step D into the same reaction kettle, stirring and dispersing until uniform, and filtering to obtain the laser ablation engraving line sealant;
the modified resin is one or two of rosin pentaerythritol ester and terpene phenolic resin;
the initiator is dicumyl peroxide, and maleic anhydride and an SEPS molecular chain are grafted through the dicumyl peroxide;
the auxiliary cross-linking agent is one or two of trimethylolpropane trimethacrylate and triallyl isocyanurate.
2. The laser ablation engraving line sealant according to claim 1, characterized in that the diblock content in the molecular chain of the SEPS (styrene-ethylene/propylene-styrene block copolymer) is equal to or less than 1%.
3. The laser ablation engraving line sealant of claim 1, wherein the antioxidant is: 2-propenoic acid-2- (1, 1-dimethylethyl) -6- [ [3- (1, 1-dimethylethyl) -2-hydroxy-5-methylphenyl ] methyl ] -4-tolyl ester, 2, 6-di-tert-butyl-p-cresol.
4. The laser ablation engraving line sealant according to claim 1, wherein the drier is one or both of copper naphthenate and potassium 2-ethylhexanoate.
5. The laser ablation engraving line sealant according to claim 1, characterized in that the mixed solvent is the following mass ratio: cyclohexane petroleum ether, acetone=3:2:1.
CN202211706073.3A 2022-12-29 2022-12-29 Laser ablation engraving line sealant Active CN116042040B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100999179A (en) * 2007-01-12 2007-07-18 张海龙 Pricking resistant, bullet-proof, leakage-proof safety tyre, its manufacturing method and its used polymer leakage-proof mending material
CN101139516A (en) * 2006-09-08 2008-03-12 张海龙 Macromolecule leak-proof mending material and leak-proof tyre containing the same
CN101845193A (en) * 2009-03-25 2010-09-29 上海日之升新技术发展有限公司 Dynamically vulcanized styrene thermoplastic elastomer and preparation method thereof
CN110527393A (en) * 2019-08-16 2019-12-03 中国航发北京航空材料研究院 A kind of Chemical milling technology for titanium alloy protection stripping lacquer
CN111073439A (en) * 2019-12-23 2020-04-28 中昊北方涂料工业研究设计院有限公司 Protective adhesive special for chemical milling of acidic media such as titanium alloy and stainless steel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101139516A (en) * 2006-09-08 2008-03-12 张海龙 Macromolecule leak-proof mending material and leak-proof tyre containing the same
CN100999179A (en) * 2007-01-12 2007-07-18 张海龙 Pricking resistant, bullet-proof, leakage-proof safety tyre, its manufacturing method and its used polymer leakage-proof mending material
CN101845193A (en) * 2009-03-25 2010-09-29 上海日之升新技术发展有限公司 Dynamically vulcanized styrene thermoplastic elastomer and preparation method thereof
CN110527393A (en) * 2019-08-16 2019-12-03 中国航发北京航空材料研究院 A kind of Chemical milling technology for titanium alloy protection stripping lacquer
CN111073439A (en) * 2019-12-23 2020-04-28 中昊北方涂料工业研究设计院有限公司 Protective adhesive special for chemical milling of acidic media such as titanium alloy and stainless steel

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