CN115073880A - Extrudable, toughened and modified polyether-ether-ketone material for aviation liquid cooling pipe system and preparation method thereof - Google Patents
Extrudable, toughened and modified polyether-ether-ketone material for aviation liquid cooling pipe system and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an extrudable, toughened and modified polyether-ether-ketone material for an aviation liquid cooling pipe system, and relates to the field of high polymer materials. The invention comprises the following components by weight: 90-95 parts of polyether-ether-ketone PEEK resin; 5-10 parts of a toughening agent PTFE; 10980.1-0.5 part of antioxidant; 0.5-0.78 parts of antioxidant S-92280.1; TR 0440.3-0.8 parts of a lubricant; 9440.2-0.5 part of light stabilizer; 0.2-0.5 part of ultraviolet absorber. Before extrusion granulation, drying the PEEK resin; and uniformly mixing the dried PEEK resin, the reinforcing agent, the antioxidant and the lubricant in proportion, adding the mixture into a double-screw extruder, melting, cooling, air drying, granulating and extruding to obtain the modified polyether-ether-ketone pipe with the corresponding specification. The modified PEEK material has the advantage of resistance to corrosion of a cooling liquid medium, has high toughness, and has excellent hot bending and other processing properties.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to an extrudable, toughened and modified polyether-ether-ketone material for an aviation liquid cooling pipe system and a preparation method thereof.
Background
The aviation liquid cooling system generally adopts a heat dissipation mode that metal aluminum pipes are used for conveying 65# cooling liquid, so that the problem of corrosion of the aluminum pipes in an alkaline working medium cannot be avoided, the service life of the pipelines is shortened, and the working efficiency of the avionic device is seriously influenced. The polyether-ether-ketone material has the characteristics of excellent high-low temperature resistance, corrosion resistance and light weight, and is widely applied to the fields of nuclear power, oil exploration, medical equipment and the like.
The direct application of Polyetheretherketone (PEEK) materials to aerospace liquid cooling piping systems faces the following problems: (1) common PEEK materials are easy to fade or expand in chemicals within-60-100 ℃, have large performance loss after being soaked for a long time, and are difficult to meet the use requirements of a liquid cooling pipe network system on mechanical performance. (2) The environmental aging resistance is weak: compared with other plastics, the pure PEEK matrix has stronger ageing resistance, but the maintaining of mechanical properties such as tensile/bending strength and the like under the long-time liquid cooling working condition still has a certain difference. Various grades of PEEK in the market are only applied to pipelines for drainage, oil and gas transmission and the like in a small amount, and have no comparability with an airborne liquid cooling pipeline. (3) The pipe fitting has poor processing performance, in order to realize the three-dimensional distribution in a narrow space in an airplane, the PEEK pipeline has good hot bending performance, and the existing polyether-ether-ketone has poor toughness and low notch impact strength, so that the phenomenon of wrinkling and cracking is easily caused during bending.
Chinese patent publication No. CN108395672A discloses a 3D-printed aramid reinforced polyetheretherketone wire and a preparation method thereof, wherein the 3D-printed aramid reinforced polyetheretherketone wire comprises the following components: 30-90 parts of polyether-ether-ketone, 10-50 parts of aramid chopped fiber, 1-10 parts of toughening agent, 1-5 parts of viscosity regulator, 1-5 parts of compatilizer, 0.05-1 part of antioxidant, 0.05-1 part of lubricant and 0-1 part of toner. The preparation method comprises the following specific steps: and uniformly stirring the polyether-ether-ketone, the toughening agent, the viscosity regulator, the compatilizer, the antioxidant, the lubricant and the toner by using a high-speed mixer, adding the mixed material into a main feeding port of a double-screw extruder, and discharging to obtain the 3D printing aramid fiber reinforced polyether-ether-ketone wire. The material has excellent strength, rigidity, elastic modulus, creep resistance, dimensional stability, heat resistance, wear resistance and other properties, is more suitable for 3D printing, and can be widely applied to the fields of medical treatment, aerospace and the like.
Chinese patent publication No. CN109320906A discloses a modified pipe of polyetheretherketone for an aviation liquid cooling system, which comprises the following components: 90-95 parts of polyether-ether-ketone PEEK resin; 5-10 parts of a nano mineral reinforcing agent; 0.3-0.7 part of antioxidant; 0.3-0.8 part of lubricant. The material has the advantage of being resistant to corrosion of a cooling liquid medium; the filling reinforcing agent is a nano mineral, so that the strength of the material is enhanced, and the coolant medium resistance of the material is not influenced; the preparation method is simple, pollution-free and easy to process.
However, the strength of the polytetrafluoroethylene tube is enhanced mainly by adding the nanoparticle reinforcing agent, but the toughness of the tube is reduced by adding light stability, the requirement of notch impact strength of an aviation pipeline system cannot be met, the processing performance of bending and the like of the tube is difficult due to the existence of the particle reinforcing body, and particularly when the bending angle is greater than 90 degrees, the tube wall is very easy to tear.
Chinese patent publication No. CN107383770A discloses a method for preparing an organic montmorillonite modified polyetheretherketone composite material, which comprises the following steps: firstly, preparing acidified ionic liquid, and then preparing porous nano silicon oxide loaded with the acidified ionic liquid; preparing organic montmorillonite; by adopting an intercalation composite technology, the porous silicon oxide loaded with the acidizing functional ionic liquid is attached to the surface of the organic montmorillonite layer, and the surface of the organic montmorillonite layer attached with the porous silicon oxide is coated in the preparation process of the polyacrylate so as to form polymethyl acrylate coated composite master batches; and finally, mixing the prepared polymethyl acrylate coated compound master batch, the polyether-ether-ketone, the lubricant and other auxiliaries, and performing high-temperature melting, screw shearing and extruding and material cutting on the mixture by using a double-screw extruder to obtain the polyether-ether-ketone composite material. The composite material has excellent mechanical property, good impact resistance and good wear resistance.
However, the forming of the polyetheretherketone pipe has high requirement on the melt index of the granules, the organic particles are reinforced and modified, and due to the problem of difficult compatibility with the basic material, the polyetheretherketone pipe is only suitable for mould pressing/extrusion molding of a plate (rod) solid section at present and also faces the problems of uneven wall thickness, difficult bending and the like of the extruded pipe and difficult subsequent processing.
Chinese patent document No. CN108395672A discloses a 3D printed aramid fiber reinforced polyetheretherketone wire and a method for preparing the same, wherein the 3D printed aramid fiber reinforced polyetheretherketone wire comprises the following components: 30-90 parts of polyether-ether-ketone, 10-50 parts of aramid chopped fiber, 1-10 parts of toughening agent, 1-5 parts of viscosity regulator, 1-5 parts of compatilizer, 0.05-1 part of antioxidant, 0.05-1 part of lubricant and 0-1 part of toner. The toughening agent can be at least one of polytetrafluoroethylene, silicon rubber, fluororubber and fluorosilicone rubber. The material has excellent strength, rigidity, elastic modulus, creep resistance, dimensional stability, heat resistance, wear resistance and other properties, is more suitable for 3D printing, and can be widely applied to the fields of medical treatment, aerospace and the like.
The patent discloses a polyether-ether-ketone wire suitable for 3D printing, and the first is that the wire is usually a small-diameter material (less than 3mm), and is not suitable for forming pipe fittings, especially large-size thin-wall pipe fittings due to the problem of wall thickness uniformity. And secondly, the material is not added with a light stabilizer and an ultraviolet absorber, so that the material is very easy to degrade under the condition of illumination or radiation, and the special use scene of the liquid cooling pipeline in the aviation high-radiation environment is difficult to meet.
Disclosure of Invention
The technical problem to be solved by the invention is how to improve the corrosion resistance, toughness and environmental aging resistance of the PEEK material.
The invention solves the technical problems through the following technical means:
the extrudable toughening modified polyether-ether-ketone material for the aviation liquid cooling pipe system comprises the following components in parts by weight: 90-95 parts of PEEK resin, 5-10 parts of toughening agent PTFE, 10980.1-0.5 part of antioxidant, S-92280.1-0.5 part of antioxidant, TR 0440.3-0.8 part of lubricant, 9440.2-0.5 part of light stabilizer and 0.2-0.5 part of ultraviolet absorber.
Has the advantages that: the composite material consists of PEEK resin, a toughening agent PTFE, an antioxidant 1098, an antioxidant S-9228, a lubricant TR044, a light stabilizer 944 and an ultraviolet absorber in special proportions, and the corrosion resistance, the toughness and the environmental aging resistance of the material are improved through the synergistic cooperation of the components.
Preferably, the PEEK resin has a melt index of 4.5g/10 min.
Preferably, the toughening agent PTFE is polytetrafluoroethylene particles with the particle size of 3-10 μm, and is subjected to surface treatment by a silane coupling agent, and the treatment steps are as follows: soaking polytetrafluoroethylene particles in absolute ethyl alcohol for 1 hour, cleaning with distilled water, removing surface stains, then placing the particles in a silane coupling agent solution with the mass fraction of 10%, and soaking for 2-5 hours at 50-70 ℃.
Preferably, the antioxidant 1098 is N, N' -bis- (3- (3, 5-di-tert-butyl-4-alkylphenyl) propionyl) hexanediamine powder.
Preferably, the antioxidant S-9228 is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite powder.
Preferably, the lubricant TR044 is a conventional lubricant.
Preferably, the light stabilizer 944 is a powder of a hindered amine light stabilizer HS ═ 944.
Preferably, the ultraviolet light absorber is UV-234 powder.
Preferably, the material is prepared by the following process: (1) drying PEEK resin for 6-8h at 120 ℃ in a drying oven, then weighing the dried PEEK resin and a toughening agent PTFE in proportion, and fully mixing the dried PEEK resin and the toughening agent PTFE in a high-speed mixer; adding the mixture into a double-screw extruder, carrying out melt blending extrusion, cooling extruded strips by cooling water, and then carrying out grain cutting in a grain cutting machine to obtain granules;
(2) placing the granules into a pipe extruder, wherein the temperature and the screw rotation speed of the pipe extruder are set as follows: the temperature of the first zone is 360-370 ℃, the temperature of the second zone is 370-380 ℃, the temperature of the third zone to the fifth zone is 380-400 ℃, the temperature of the sixth zone to the ninth zone is 370-380 ℃, the temperature of the machine head is 380-400 ℃, and the rotating speed of the screw is controlled at 380-420 rpm; and (3) installing a matched extrusion molding die according to the requirement of the outer diameter size, and extruding the polyether-ether-ketone pipe with the corresponding specification.
The invention also provides a preparation method of the extrudable, toughened and modified polyether-ether-ketone material for the aviation liquid cooling pipe system, which comprises the following steps:
(1) drying PEEK resin for 6-8h at 120 ℃ in a drying oven, then weighing the dried PEEK resin and a toughening agent PTFE in proportion, and fully mixing the dried PEEK resin and the toughening agent PTFE in a high-speed mixer; adding the mixture into a double-screw extruder, carrying out melt blending extrusion, cooling extruded strips by cooling water, and then carrying out grain cutting in a grain cutting machine to obtain granules;
(2) the pellets were placed in a pipe extruder, the temperature and screw speed of which were set as follows: the temperature of the first zone is 360-370 ℃, the temperature of the second zone is 370-380 ℃, the temperature of the third zone to the fifth zone is 380-400 ℃, the temperature of the sixth zone to the ninth zone is 370-380 ℃, the temperature of the machine head is 380-400 ℃, and the rotating speed of the screw is controlled at 380-420 rpm; and (3) installing a matched extrusion molding die according to the requirement of the outer diameter size, and extruding the polyether-ether-ketone pipe with the corresponding specification.
The invention has the advantages that: the PEEK resin has the advantage of resistance to corrosion of a cooling liquid medium, and does not have color difference after being soaked for a long time; the pipe has higher toughness, and meanwhile, the strength loss does not influence the use of the pipe in a liquid cooling environment; the anti-aging performance is high; and the melt index of the material meets the requirement of the extrusion molding property of the pipe.
Drawings
FIG. 1 is a schematic view of the PEEK material before and after modification immersed in 65# coolant;
FIG. 2 is a schematic view of the mechanical properties of the toughened and modified PEEK material of example 1 after being soaked in 65# cooling liquid;
FIG. 3 is a schematic view of the mechanical properties of the toughened and modified PEEK material of example 2 after being soaked in 65# cooling liquid.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the extrudable toughening modified polyether-ether-ketone material for the aviation liquid cooling pipe system comprises the following components in parts by weight: 90 parts of polyether-ether-ketone PEEK resin, 5 parts of toughening agent PTFE, 10980.1 parts of antioxidant, S-92280.1 parts of antioxidant, TR 0440.3 parts of lubricant, 9440.2 parts of light stabilizer and 0.2 part of ultraviolet light absorber.
The PEEK resin has the melt index of 4.5g/10min, and is suitable for pipe extrusion; the toughening agent PTFE is polytetrafluoroethylene particles with the particle size of 3-10 mu m, the surface of the toughening agent PTFE is treated by a silane coupling agent, and the antioxidant 1098 is N, N' -bis- (3- (3, 5-di-tert-butyl-4-alkyl phenyl) propionyl) hexanediamine powder; antioxidant S-9228 is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite powder; lubricant TR044 is a conventional lubricant; the light stabilizer 944 is hindered amine light stabilizer HS ═ 944 powder; the ultraviolet light absorber is UV-234 powder.
The preparation method of the extrudable, toughened and modified polyether-ether-ketone material for the aviation liquid cooling pipe system comprises the following steps of:
(1) drying PEEK resin for 6 hours at 120 ℃ in a drying oven, then weighing the dried PEEK resin and a toughening agent PTFE in proportion, and fully mixing the dried PEEK resin and the toughening agent PTFE in a high-speed mixer; adding the mixture into a double-screw extruder, carrying out melt blending extrusion, cooling extruded strips by cooling water, and then carrying out grain cutting in a grain cutting machine to obtain granules;
(2) placing the granules into a pipe extruder, wherein the temperature and the screw rotation speed of the pipe extruder are set as follows: 360 ℃ in the first area, 370 ℃ in the second area, 380 ℃ in the third area to the fifth area, 370 ℃ in the sixth area to the ninth area, 380 ℃ at the head temperature, and 380rpm at the screw rotation speed; and (3) installing an extrusion molding die with the outer diameter of 12mm and the inner diameter of 10mm according to the requirement of the outer diameter size, and extruding the polyether-ether-ketone pipe with the corresponding specification.
After the PEEK granules prepared in the embodiment are placed in a 100 ℃ oven to be dried for 24 hours, a national standard sample strip is injected and tested, and the properties of the PEEK granules, such as the national standard tensile strength, the national standard bending modulus, the national standard cantilever beam notch impact strength and the like, are tested, wherein the injection temperature is 370-380 ℃ and the mold temperature is 170-190 ℃.
Example 2:
the extrudable toughening modified polyether-ether-ketone material for the aviation liquid cooling pipe system comprises the following components in parts by weight: 95 parts of polyether-ether-ketone PEEK resin, 10 parts of toughening agent PTFE, 10980.5 parts of antioxidant, S-92280.5 parts of antioxidant, TR 0440.8 parts of lubricant, 9440.5 parts of light stabilizer and 0.5 part of ultraviolet light absorber.
The PEEK resin has the melt index of 4.5g/10min, and is suitable for pipe extrusion; the toughening agent PTFE is polytetrafluoroethylene particles with the particle size of 3-10 mu m, and is subjected to surface treatment by a silane coupling agent, and the antioxidant 1098 is N, N' -bis- (3- (3, 5-di-tert-butyl-4-alkyl phenyl) propionyl) hexamethylene diamine powder; the antioxidant S-9228 is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite powder; lubricant TR044 is a conventional lubricant; the light stabilizer 944 is hindered amine light stabilizer HS ═ 944 powder; the ultraviolet light absorber is UV-234 powder.
The preparation method of the extrudable, toughened and modified polyether-ether-ketone material for the aviation liquid cooling pipe system comprises the following steps of:
(1) drying PEEK resin in an oven at 100 ℃ for 8 hours, then weighing the dried PEEK resin and a toughening agent PTFE in proportion, and fully mixing the dried PEEK resin and other auxiliaries in a high-speed mixer; adding the mixture into a double-screw extruder, carrying out melt blending extrusion, cooling extruded strips by cooling water, and then pelletizing in a pelletizer to obtain pellets;
(2) placing the granules into a pipe extruder, wherein the temperature and the screw rotation speed of the pipe extruder are set as follows: 370 ℃ in the first area, 380 ℃ in the second area, 400 ℃ in the third area to the fifth area, 380 ℃ in the sixth area to the ninth area, 400 ℃ in the head temperature and 420rpm in the rotating speed of the screw; and (3) installing an extrusion molding die with the outer diameter of 12mm and the inner diameter of 10mm according to the requirement of the outer diameter size, and extruding the polyether-ether-ketone pipe with the corresponding specification.
After the PEEK granules prepared in the embodiment are placed in a 100 ℃ oven to be dried for 24 hours, a national standard sample strip is injected and tested, and the properties of the PEEK granules, such as the national standard tensile strength, the national standard bending modulus, the national standard cantilever beam notch impact strength and the like, are tested, wherein the injection temperature is 370-380 ℃ and the mold temperature is 170-190 ℃.
Example 3:
the extrudable toughening modified polyether-ether-ketone material for the aviation liquid cooling pipe system comprises the following components in parts by weight: 92 parts of polyether-ether-ketone PEEK resin, 8 parts of toughening agent PTFE, 10980.3 parts of antioxidant, S-92280.3 parts of antioxidant, TR 0440.5 parts of lubricant, 9440.4 parts of light stabilizer and 0.4 part of ultraviolet light absorber.
The PEEK resin has the melt index of 4.5g/10min, and is suitable for pipe extrusion; the toughening agent PTFE is polytetrafluoroethylene particles with the particle size of 3-10 mu m, and is subjected to surface treatment by a silane coupling agent, and the antioxidant 1098 is N, N' -bis- (3- (3, 5-di-tert-butyl-4-alkyl phenyl) propionyl) hexamethylene diamine powder; antioxidant S-9228 is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite powder; lubricant TR044 is a conventional lubricant; the light stabilizer 944 is hindered amine light stabilizer HS ═ 944 powder; the ultraviolet light absorber is UV-234 powder.
The preparation method of the extrudable, toughened and modified polyether-ether-ketone material for the aviation liquid cooling pipe system comprises the following steps of:
(1) drying PEEK resin in an oven at 150 ℃ for 7h, then weighing the dried PEEK resin and a toughening agent PTFE in proportion, and fully mixing the dried PEEK resin and other auxiliaries in a high-speed mixer; adding the mixture into a double-screw extruder, carrying out melt blending extrusion, cooling extruded strips by cooling water, and then pelletizing in a pelletizer to obtain pellets;
(2) placing the granules into a pipe extruder, wherein the temperature and the screw rotation speed of the pipe extruder are set as follows: the temperature of the first zone is 365 ℃, the temperature of the second zone is 375 ℃, the temperature of the third zone to the fifth zone is 390 ℃, the temperature of the sixth zone to the ninth zone is 375 ℃, the temperature of the machine head is 390 ℃, and the rotating speed of the screw is controlled at 400 rpm; and (3) installing an extrusion molding die with the outer diameter of 12mm and the inner diameter of 10mm according to the requirement of the outer diameter size, and extruding the polyether-ether-ketone pipe with the corresponding specification.
After the PEEK granules prepared in the embodiment are placed in a 100 ℃ oven to be dried for 24 hours, a national standard sample strip is injected and tested, and the properties of the PEEK granules, such as the national standard tensile strength, the national standard bending modulus, the national standard cantilever beam notch impact strength and the like, are tested, wherein the injection temperature is 370-380 ℃ and the mold temperature is 170-190 ℃.
And (3) drying the unmodified PEEK granules in a 100 ℃ oven for 24 hours, then, injection molding a national standard sample strip, and testing the properties of the PEEK granules, such as the national standard tensile strength, the national standard bending modulus, the national standard cantilever beam notch impact strength and the like, wherein the injection molding temperature is 370-380 ℃ and the mold temperature is 170-190 ℃.
The results of testing unmodified PEEK with examples 1-3 are shown in table 1 below:
TABLE 1
As can be seen from Table 1, the impact strength of the simply supported beam notch of the toughened and modified PEEK material is remarkably improved, and the strength loss is small.
The pipes obtained in examples 1 and 2 were immersed in 65# cooling liquid at 70 ℃ for 0 to 2500 hours, respectively, and the physical properties thereof were measured.
As can be seen from FIG. 1, the color of the PEEK material before modification is whitish after being soaked in a cooling liquid for a long time, but the color of the modified PEEK material is unchanged before and after being soaked.
As can be seen from fig. 2, after a long time of soaking, the strength index of the modified polyetheretherketone material of example 1 is not significantly changed.
As can be seen from FIG. 3, the strength index of the modified material of example 2 did not change significantly after a long-term immersion.
Therefore, the pipes prepared in the embodiment 1 and the embodiment 2 have better coolant corrosion resistance in the coolant material.
To further illustrate the rationality of the formulation, the following examples were conducted to perform a series of strength comparison tests by adjusting the amount of the toughening agent polytetrafluoroethylene particles.
Example 4:
the extrudable toughening modified polyether-ether-ketone material for the aviation liquid cooling pipe system comprises the following components in parts by weight: 90 parts of polyether-ether-ketone PEEK resin, 3 parts of toughening agent PTFE, 10980.1 parts of antioxidant, S-92280.1 parts of antioxidant, TR 0440.3 parts of lubricant, 9440.2 parts of light stabilizer and 0.2 part of ultraviolet absorber.
The melt index of the PEEK resin is 4.5g/10min, and the PEEK resin is suitable for pipe extrusion; the toughening agent PTFE is polytetrafluoroethylene particles with the particle size of 3-10 mu m, and is subjected to surface treatment by a silane coupling agent, and the antioxidant 1098 is N, N' -bis- (3- (3, 5-di-tert-butyl-4-alkyl phenyl) propionyl) hexamethylene diamine powder; antioxidant S-9228 is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite powder; lubricant TR044 is a conventional lubricant; the light stabilizer 944 is hindered amine light stabilizer HS ═ 944 powder; the ultraviolet light absorber is UV-234 powder.
The preparation method of the extrudable, toughened and modified polyether-ether-ketone material for the aviation liquid cooling pipe system comprises the following steps of:
(1) drying PEEK resin for 6 hours at 120 ℃ in a drying oven, then weighing the dried PEEK resin and a toughening agent PTFE in proportion, and fully mixing the dried PEEK resin and the toughening agent PTFE in a high-speed mixer; adding the mixture into a double-screw extruder, carrying out melt blending extrusion, cooling extruded strips by cooling water, and then carrying out grain cutting in a grain cutting machine to obtain granules;
(2) placing the granules into a pipe extruder, wherein the temperature and the screw rotation speed of the pipe extruder are set as follows: 360 ℃ in the first area, 370 ℃ in the second area, 380 ℃ in the third area to the fifth area, 370 ℃ in the sixth area to the ninth area, 380 ℃ at the head temperature, and 380rpm at the screw rotation speed; and (3) installing an extrusion molding die with the outer diameter of 12mm and the inner diameter of 10mm according to the requirement of the outer diameter size, and extruding the polyether-ether-ketone pipe with the corresponding specification.
After the PEEK granules prepared in the embodiment are placed in a 100 ℃ drying oven to be dried for 24 hours, a national standard sample strip is injected, and the properties such as the national standard tensile strength, the bending modulus, the cantilever beam notch impact strength and the like are tested, wherein the injection molding temperature is 370-380 ℃, and the mold temperature is 170-190 ℃.
Example 5:
the extrudable toughening modified polyether-ether-ketone material for the aviation liquid cooling pipe system comprises the following components in parts by weight: 90 parts of polyether-ether-ketone PEEK resin, 13 parts of toughening agent PTFE, 10980.1 parts of antioxidant, S-92280.1 parts of antioxidant, TR 0440.3 parts of lubricant, 9440.2 parts of light stabilizer and 0.2 part of ultraviolet absorber.
The PEEK resin has the melt index of 4.5g/10min, and is suitable for pipe extrusion; the toughening agent PTFE is polytetrafluoroethylene particles with the particle size of 3-10 mu m, and is subjected to surface treatment by a silane coupling agent, and the antioxidant 1098 is N, N' -bis- (3- (3, 5-di-tert-butyl-4-alkyl phenyl) propionyl) hexamethylene diamine powder; antioxidant S-9228 is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite powder; lubricant TR044 is a conventional lubricant; the light stabilizer 944 is hindered amine light stabilizer HS ═ 944 powder; the ultraviolet light absorber is UV-234 powder.
The preparation method of the extrudable, toughened and modified polyether-ether-ketone material for the aviation liquid cooling pipe system comprises the following steps of:
(1) drying PEEK resin for 6 hours at 120 ℃ in a drying oven, then weighing the dried PEEK resin and a toughening agent PTFE in proportion, and fully mixing the dried PEEK resin and the toughening agent PTFE in a high-speed mixer; adding the mixture into a double-screw extruder, carrying out melt blending extrusion, cooling extruded strips by cooling water, and then carrying out grain cutting in a grain cutting machine to obtain granules;
(2) placing the granules into a pipe extruder, wherein the temperature and the screw rotation speed of the pipe extruder are set as follows: 360 ℃ in the first area, 370 ℃ in the second area, 380 ℃ in the third area to the fifth area, 370 ℃ in the sixth area to the ninth area, 380 ℃ at the head temperature, and 380rpm at the screw rotation speed; and (3) installing an extrusion molding die with the outer diameter of 12mm and the inner diameter of 10mm according to the requirement of the outer diameter size, and extruding the polyether-ether-ketone pipe with the corresponding specification.
After the PEEK granules prepared in the embodiment are placed in a 100 ℃ drying oven to be dried for 24 hours, a national standard sample strip is injected, and the properties such as the national standard tensile strength, the bending modulus, the cantilever beam notch impact strength and the like are tested, wherein the injection molding temperature is 370-380 ℃, and the mold temperature is 170-190 ℃.
Example 6:
the extrudable toughening modified polyether-ether-ketone material for the aviation liquid cooling pipe system comprises the following components in parts by weight: 90 parts of polyether-ether-ketone PEEK resin, 15 parts of toughening agent PTFE, 10980.1 parts of antioxidant, S-92280.1 parts of antioxidant, TR 0440.3 parts of lubricant, 9440.2 parts of light stabilizer and 0.2 part of ultraviolet absorber.
The PEEK resin has the melt index of 4.5g/10min, and is suitable for pipe extrusion; the toughening agent PTFE is polytetrafluoroethylene particles with the particle size of 3-10 mu m, and is subjected to surface treatment by a silane coupling agent, and the antioxidant 1098 is N, N' -bis- (3- (3, 5-di-tert-butyl-4-alkyl phenyl) propionyl) hexamethylene diamine powder; antioxidant S-9228 is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite powder; lubricant TR044 is a conventional lubricant; the light stabilizer 944 is hindered amine light stabilizer HS ═ 944 powder; the ultraviolet light absorber is UV-234 powder.
The preparation method of the extrudable, toughened and modified polyether-ether-ketone material for the aviation liquid cooling pipe system comprises the following steps of:
(1) drying PEEK resin for 6 hours at 120 ℃ in a drying oven, then weighing the dried PEEK resin and a toughening agent PTFE in proportion, and fully mixing the dried PEEK resin and the toughening agent PTFE in a high-speed mixer; adding the mixture into a double-screw extruder, carrying out melt blending extrusion, cooling extruded strips by cooling water, and then carrying out grain cutting in a grain cutting machine to obtain granules;
(2) placing the granules into a pipe extruder, wherein the temperature and the screw rotation speed of the pipe extruder are set as follows: 360 ℃ in the first area, 370 ℃ in the second area, 380 ℃ in the third area to the fifth area, 370 ℃ in the sixth area to the ninth area, 380 ℃ at the head temperature and 380 ℃ at the screw rotation speed of 380 rpm; and (3) installing an extrusion molding die with the outer diameter of 12mm and the inner diameter of 10mm according to the requirement of the outer diameter size, and extruding the polyether-ether-ketone pipe with the corresponding specification.
After the PEEK granules prepared in the embodiment are placed in a 100 ℃ oven to be dried for 24 hours, a national standard sample strip is injected and tested, and the properties of the PEEK granules, such as the national standard tensile strength, the national standard bending modulus, the national standard cantilever beam notch impact strength and the like, are tested, wherein the injection temperature is 370-380 ℃ and the mold temperature is 170-190 ℃.
The test results for examples 4-6 are shown in table 2 below:
TABLE 2
As can be seen from Table 2, in example 4, the improvement of the impact strength is limited due to the small amount of the toughening agent PTFE; while the impact strength is improved along with the increase of the PTFE part of the toughening agent, the tensile bending strength loss is obvious, such as example 5 and example 6, the more the PTFE part is in engineering application, the more difficult the dispersion is, and therefore, the PTFE part of the toughening agent is 5-10.
Comparative example 1:
example 1 described in the specification of chinese patent application publication No. CN109320906A was used as comparative example 1 of the present application, that is:
a modified pipe of polyether-ether-ketone for an aviation liquid cooling system comprises 94 parts of PEEK resin, 5 parts of reinforcing agent nano montmorillonite, 0.5 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate and 0.5 part of lubricant pentaerythritol stearate by weight.
Other embodiments are the same as in example 1 of the present application.
And (3) drying the PEEK granules prepared in the comparative example in a 100 ℃ oven for 24 hours, then carrying out injection molding on a national standard sample strip, and testing the properties of the PEEK granules, such as the national standard tensile strength, the national standard bending modulus, the national standard cantilever beam notch impact strength and the like, wherein the injection molding temperature is 370-380 ℃ and the mold temperature is 170-190 ℃.
Comparative example 2:
example 2 described in the specification of chinese patent application publication No. CN109320906A was used as comparative example 2 of the present application, namely:
a modified pipe of polyether-ether-ketone for an aviation liquid cooling system comprises 90 parts of PEEK resin, 9 parts of reinforcing agent calcium carbonate, 0.7 part of antioxidant tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 0.3 part of lubricant N-N-hexamethylene bis-stearamide by weight.
Other embodiments are the same as in example 1 of the present application.
And (3) drying the PEEK granules prepared in the comparative example in a 100 ℃ oven for 24 hours, then carrying out injection molding on a national standard sample strip, and testing the properties of the PEEK granules, such as the national standard tensile strength, the national standard bending modulus, the national standard cantilever beam notch impact strength and the like, wherein the injection molding temperature is 370-380 ℃ and the mold temperature is 170-190 ℃.
The test results of examples 1-6 and comparative examples 1-2 are shown in Table 3 below:
TABLE 3
As can be seen from Table 3, although the tensile flexural strength of the material is greatly improved by the addition of the reinforcing agent in the comparative example, the impact properties are seriously impaired. In an aviation liquid cooling pipeline, due to the spatial three-dimensional bending characteristic of a pipe network, the pipeline is required to have good hot bending formability, certain engineering realizability is achieved only if higher toughness, namely impact index, is met, and the higher the tensile strength is, the poorer the toughness is.
Comparative example 3:
the extrudable toughening modified polyether-ether-ketone material for the aviation liquid cooling pipe system comprises the following components in parts by weight: 90 parts of polyether-ether-ketone PEEK resin, 5 parts of toughening agent PTFE, 10980.1 parts of antioxidant, S-92280.1 parts of antioxidant, TR 0440.3 parts of lubricant and 0.2 part of ultraviolet absorber.
Other embodiments are the same as in example 1 of the present application, and in this comparative example, the light stabilizer 944 is absent as compared to example 1.
And (3) drying the PEEK granules prepared in the comparative example in a 100 ℃ oven for 24 hours, then carrying out injection molding on a national standard sample strip, and testing the properties of the PEEK granules, such as the national standard tensile strength, the national standard bending modulus, the national standard cantilever beam notch impact strength and the like, wherein the injection molding temperature is 370-380 ℃ and the mold temperature is 170-190 ℃.
The bars of examples 1-6 and comparative example 3 were subjected to a UV-A test to evaluate short-term high-dose light aging performance. Irradiance: (0.55 shi 0.02) W/(m2 nm) @340 nm; exposure period: drying for 102min, and spraying for 18 min; total radiant quantity: 2500KJ/m 2.
The test results are shown in table 4 below:
TABLE 4
As can be seen from Table 4 above, since no light stabilizer is added in comparative example 3, after a large dose of irradiation in a short time, the strength and toughness indexes of the material are greatly reduced, and the molecular decomposition is locally generated on the surface of the material, and the wrinkling is caused by the breakage of the molecular chain.
Comparative example 4:
the extrudable toughening modified polyether-ether-ketone material for the aviation liquid cooling pipe system comprises the following components in parts by weight: 90 parts of polyether-ether-ketone PEEK resin, 5 parts of toughening agent PTFE, 10980.1 parts of antioxidant, S-92280.1 parts of antioxidant, TR 0440.3 parts of lubricant and 9440.2 parts of light stabilizer.
Other embodiments are the same as in example 1 of the present application, and this comparative example lacks an ultraviolet light absorber as compared to example 1.
And (3) drying the PEEK granules prepared in the comparative example in a 100 ℃ oven for 24 hours, then carrying out injection molding on a national standard sample strip, and testing the properties of the PEEK granules, such as the national standard tensile strength, the national standard bending modulus, the national standard cantilever beam notch impact strength and the like, wherein the injection molding temperature is 370-380 ℃ and the mold temperature is 170-190 ℃.
The test pieces of examples 1 to 6 and comparative example 4 were placed in a UV aging test chamber and the aging properties under UV light (central wavelength 340nm) were evaluated for a long period of time (720 hours).
The test results are shown in table 5 below:
TABLE 5
As can be seen from the above Table 5, since the UV absorber is not added in the comparative example 4, the strength and toughness indexes of the material are obviously reduced after long-term UV irradiation, and the surface of the material is locally degraded by molecules and whitened.
The above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The extrudable toughening modified polyether-ether-ketone material for the aviation liquid cooling pipe system is characterized by comprising the following components in parts by weight: 90-95 parts of PEEK resin, 5-10 parts of toughening agent PTFE, 10980.1-0.5 part of antioxidant, S-92280.1-0.5 part of antioxidant, TR 0440.3-0.8 part of lubricant, 9440.2-0.5 part of light stabilizer and 0.2-0.5 part of ultraviolet absorber.
2. The extrudable toughened modified polyetheretherketone material as claimed in claim 1, wherein the PEEK resin has a melt index of 4.5g/10 min.
3. The extrudable toughening modified polyether ether ketone material for the aviation liquid cooling pipe system as claimed in claim 1, wherein the toughening agent PTFE is polytetrafluoroethylene particles with the particle size of 3-10 μm, and is subjected to surface treatment by a silane coupling agent, and the treatment steps are as follows: soaking polytetrafluoroethylene particles in absolute ethyl alcohol for 1 hour, cleaning with distilled water, removing surface stains, then placing the particles in a silane coupling agent solution with the mass fraction of 10%, and soaking for 2-5 hours at 50-70 ℃.
4. The extrudable, toughened and modified polyetheretherketone material for an aviation liquid cooling pipe system as claimed in claim 3, wherein the antioxidant 1098 is N, N' -bis- (3- (3, 5-di-tert-butyl-4-alkylphenyl) propionyl) hexanediamine powder.
5. The extrudable, toughened and modified polyetheretherketone material for an aviation liquid cooling pipe system as claimed in claim 1, wherein the antioxidant S-9228 is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite powder.
6. The extrudable, toughened and modified polyetheretherketone material for an aviation liquid cooling pipe system as claimed in claim 1, wherein the lubricant TR044 is a conventional lubricant.
7. The extrudable, toughened and modified polyetheretherketone material for an aviation liquid cooling pipe system as claimed in claim 1, wherein the light stabilizer 944 is a hindered amine light stabilizer HS 944 powder.
8. The extrudable, toughened and modified polyetheretherketone material for an aviation liquid cooling pipe system as claimed in claim 7, wherein the ultraviolet absorber is UV-234 powder.
9. The extrudable, toughened and modified polyether ether ketone material for the aviation liquid cooling pipe system as claimed in claim 1, wherein the material is prepared by the following process: (1) drying PEEK resin in an oven at the temperature of 100-150 ℃ for 6-8h, then weighing the dried PEEK resin and a toughening agent PTFE in proportion, and fully mixing the dried PEEK resin and the toughening agent PTFE in a high-speed mixer; adding the mixture into a double-screw extruder, carrying out melt blending extrusion, cooling extruded strips by cooling water, and then carrying out grain cutting in a grain cutting machine to obtain granules;
(2) placing the granules into a pipe extruder, wherein the temperature and the screw rotation speed of the pipe extruder are set as follows: the temperature of the first zone is 360-370 ℃, the temperature of the second zone is 370-380 ℃, the temperature of the third zone to the fifth zone is 380-400 ℃, the temperature of the sixth zone to the ninth zone is 370-380 ℃, the temperature of the machine head is 380-400 ℃, and the rotating speed of the screw is controlled at 380-420 rpm; and (3) installing a matched extrusion molding die according to the requirement of the outer diameter size, and extruding the polyether-ether-ketone pipe with the corresponding specification.
10. The preparation method of the extrudable toughened modified polyetheretherketone material for the aviation liquid cooling pipe system as claimed in any one of claims 1 to 8, which comprises the following steps:
(1) drying PEEK resin in an oven at 100-150 ℃ for 6-8h, then weighing the dried PEEK resin and a toughening agent PTFE in proportion, and fully mixing the dried PEEK resin and other auxiliaries in a high-speed mixer; adding the mixture into a double-screw extruder, carrying out melt blending extrusion, cooling extruded strips by cooling water, and then carrying out grain cutting in a grain cutting machine to obtain granules;
(2) placing the granules into a pipe extruder, wherein the temperature and the screw rotation speed of the pipe extruder are set as follows: the temperature of the first zone is 360-370 ℃, the temperature of the second zone is 370-380 ℃, the temperature of the third zone to the fifth zone is 380-400 ℃, the temperature of the sixth zone to the ninth zone is 370-380 ℃, the temperature of the machine head is 380-400 ℃, and the rotating speed of the screw is controlled at 380-420 rpm; and (3) installing a matched extrusion molding die according to the requirement of the outer diameter size, and extruding the polyether-ether-ketone pipe with the corresponding specification.
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