CN113214599B - PEEK bar and processing technology thereof - Google Patents
PEEK bar and processing technology thereof Download PDFInfo
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Abstract
The invention discloses a PEEK bar and a processing technology thereof. The bar material firstly washes the E-CR glass fiber with acid solution to remove the convex part with poor surface binding force, deepens the etching of the groove and hole structure on the surface of the E-CR glass fiber; then, nano Al is added2O3Coating the surface of the E-CR glass fiber to increase the surface roughness and the surface area; KH-550/KH-602 mixed coupling agent is selected to modify the surface of the E-CR glass fiber, and the coupling agent is used as a molecular bridge between the E-CR glass fiber and organic resin to improve the interfacial property between the composite materials; modified polyetheretherketone/nano Al is prepared by the modified E-CR glass fiber and modified polyetheretherketone powder through the processes of blending melting and injection molding2O3a/E-CR glass fiber composite bar stock; compared with the polyether-ether-ketone raw material, the wear resistance, the acid and alkali corrosion resistance, the toughness and the thermal stability of the material are improved to different degrees, the preparation process flow is simple, the processing cost is low, and the material is suitable for bars in high-temperature and strong acid and alkali corrosion environments.
Description
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to a PEEK bar and a processing technology thereof.
Background
With the continuous development of science and technology in China, industrial materials are continuously updated, and the industrial materials are developed from the earliest cast iron bars, galvanized steel bars and the like to the current thermosetting and thermoplastic plastic bars such as PPR, PVC, UPVC, ABS plastics and the like so as to be suitable for various complex environments.
The polyetheretherketone is used as semi-crystalline aromatic thermoplastic resin, is extremely excellent engineering plastic, has the characteristics of strong high temperature resistance, acid and alkali corrosion resistance, high strength, high toughness and the like, is widely used in the engineering of aerospace, medical treatment, chemistry, automobiles and the like, and is highly dependent on various industries.
Meanwhile, in order to adapt to the future development trend and meet the requirement of modern science and technology on higher standard of materials, people continuously modify the polyetheretherketone and compound the polyetheretherketone with different inorganic materials to prepare a material with higher quality, continuously improve the heat resistance, corrosion resistance, mechanical strength and toughness of the material and reduce the friction coefficient.
Disclosure of Invention
The invention aims to provide a PEEK bar and a processing technology thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a processing technology of a PEEK bar comprises the following steps:
(1) soaking the E-CR glass fiber in a medium-strength acid solution, heating in a water bath at 40-60 ℃, stirring and ultrasonically treating for 2-4h, cleaning residual acid radical ions on the surface of the E-CR glass fiber with deionized water after filtering, and drying in a vacuum drying oven to obtain the pretreated E-CR glass fiber. The E-CR glass fiber is boron-free alkali-free glass fiber, has strong acid resistance and alkali resistance, and can improve the heat resistance, corrosion resistance and mechanical strength of the material when used as a reinforcing agent of polyether-ether-ketone; E-CR glass fibers consisting essentially of SiO2、CaO、Al2O3MgO, which is treated by acidification with medium-strong acid to remove the oxide with weaker surface bonding force, thereby etching the surface of the E-CR glass fiber, increasing the surface roughness and further enhancing the mechanical contact between the glass fiber and the resin; and the surface activity of the glass fiber can be enhanced through acid washing modification, so that the density of the surface silicon hydroxyl groups is increased.
(2) Adding pretreated E-CR glass fiber and potassium hexametaphosphate into deionized water, stirring and ultrasonically dispersing, adding aluminum sulfate to form a suspension, heating in a water bath to 70-120 ℃, dropwise adding sulfuric acid and potassium hydroxide solution, adjusting the pH value to 4.5-6, reacting for 0.5-1h, filtering, washing residual sulfate ions on the surface with deionized water, and drying in a vacuum drying oven to obtain the nano Al2O3a/E-CR glass fiber material; silicon hydroxyl on the surface of the pretreated E-CR glass fiber is beneficial to uniform coating of nano-alumina, and the introduction of nano-ions increases the roughness and the specific surface area of the E-CR glass fiber, so that the interface bonding capability of the composite material can be improved; and nano Al2O3The filler can increase the toughness and the wear resistance of the material.
(3) Dispersing silane coupling agent in ethanol, stirring to regulate pH value, adding nano Al2O3Performing ultrasonic dispersion on the E-CR glass fiber for 0.5 to 1 hour, performing reflux reaction for 6 to 10 hours at the temperature of between 75 and 85 ℃, filtering, cleaning and drying to obtain the modified nano Al2O3E-CR glass fibers; the modification of the KH-550/KH-602 silane coupling agent is mainly realized by that one end of the coupling agent molecule is an ether bond short chain and is connected with nano Al2O3The surface of the/E-CR glass fiber is subjected to dehydration condensation, and the other isThe amino-terminated bond is combined with the acid group of the sulfonated polyether ether ketone, so that the inorganic group of the composite material is effectively combined with the resin; the KH-602 diamino functional group structure is helpful for modifying nano Al2O3the/E-CR glass fiber is combined with resin, while the strong thermal stability of KH-550 is beneficial to the reaction at high temperature, and the coupling effect of KH-550/KH-602 mixed silane coupling agent is more obvious than that of single use.
(4) Sulfonated polyether ether ketone with sulfonation degree of 45-70 percent and modified nano Al2O3Putting the E-CR glass fiber and the aluminum dihydrogen phosphate into a reaction vessel, uniformly stirring and drying, putting into a double-screw extruder, performing melt extrusion, cooling and demolding, and performing injection molding to obtain a PEEK bar material; sulfonic acid groups are introduced into the polyether-ether-ketone through sulfonated side chains, and the introduction of polar groups can enhance the hydrophilicity of the resin, so that the blending effect of the inorganic filler and the resin matrix is improved; under the condition of high temperature, the alumina and the nano alumina in the glass fiber are contacted with inorganic phosphate, and Al2O3Aluminum ions in the composite material destroy P-O-P bonds of inorganic phosphate and form Al-O-P bonds, so that the phosphate network structure is contracted, pores and cracks of the composite material are reduced, and the thermal stability and the mechanical property of the composite material are improved; the E-CR glass fiber is used as a reinforcing agent, so that the corrosion resistance and the high temperature resistance of the composite material can be effectively enhanced;
further, the strong acid solution in the step (1) is one of oxalic acid, pyruvic acid and phosphoric acid.
Further, the silane coupling agent in the step (3) is a mixed coupling agent of KH-550 (80-90%), KH-602 (10-20%).
Further, the temperature of each zone of the double-screw extruder in the step (4) is as follows: the first zone 345-355 ℃, the second zone 355-365 ℃, the third zone to the fifth zone 365-375 ℃, the sixth zone to the ninth zone 375-385 ℃, the head temperature 365-375 ℃, and the screw rotation speed: 320-.
Further, the bar includes: sulfonated polyether ether ketone and modified nano Al2O3The mass ratio of the E-CR glass fiber to the aluminum dihydrogen phosphate is 1: (0.2-0.3): (0.4-0.6).
Further, the modified nano Al2O3E-CR glassThe fiber is made of nano Al2O3the/E-CR glass fiber is prepared by coating a coupling agent, and the coating mass ratio is (1-2%).
Further, the nano Al2O3The raw materials of each component of the E-CR glass fiber comprise: the mass ratio of the pretreated E-CR glass fiber to the potassium hexametaphosphate to the aluminum sulfate is 1: (0.03-0.05): (0.1-0.3).
Further, the pretreated E-CR glass fiber is obtained by acidifying the surface of the E-CR glass fiber.
Compared with the prior art, the invention has the following beneficial effects:
the bar material is prepared by compounding E-CR glass fiber, nano aluminum oxide and aluminum dihydrogen phosphate serving as reinforcing agents and polyether-ether-ketone2O3a/E-CR fiberglass composite; acid washing and nano Al treatment of E-CR glass fiber2O3The coating and mixed silane coupling agent surface treatment enhances the interface bonding force with the resin base, and the E-CR glass fiber is used as a reinforcing agent, so that the corrosion resistance and the high temperature resistance of the composite material can be effectively enhanced; the phosphate aluminum dihydrogen phosphate firstly reacts with alumina in the inorganic filler at high temperature, so that the network structure of the phosphate is contracted, the pores and cracks of the composite material are reduced, and the thermal stability and the mechanical property of the composite material are improved; nano Al2O3The filler can increase the toughness and the wear resistance of the material; the introduction of the polar group can enhance the hydrophilicity of the resin, thereby improving the blending effect of the inorganic filler and the resin matrix. The invention relates to a composite nano Al after being modified by sulfonated polyether-ether-ketone2O3The heat resistance, corrosion resistance, mechanical strength and toughness of the material are improved, and the friction coefficient is reduced.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and 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
(1) And (3) soaking the E-CR glass fiber in an oxalic acid solution, heating in a water bath at 40 ℃, stirring and ultrasonically treating for 2 hours, cleaning residual acid radical ions on the surface of the E-CR glass fiber with deionized water after filtering, and drying in a vacuum drying oven to obtain the pretreated E-CR glass fiber.
(2) Adding pretreated E-CR glass fiber and potassium hexametaphosphate into deionized water, stirring and ultrasonically dispersing, adding aluminum sulfate to form a suspension, heating in a water bath to 70 ℃, dropwise adding sulfuric acid and potassium hydroxide solution, adjusting the pH value to 4.5, reacting for 0.5h, filtering, washing residual sulfate ions on the surface with deionized water, and drying in a vacuum drying oven to obtain the nano Al2O3a/E-CR glass fiber material.
(3) Dispersing silane coupling agent in ethanol, stirring to regulate pH value, adding nano Al2O3Performing ultrasonic dispersion on the/E-CR glass fiber for 0.5h, performing reflux reaction for 6h at the temperature of 75 ℃, filtering, cleaning and drying to obtain the modified nano Al2O3E-CR glass fibers;
(4) 30g of sulfonated polyether ether ketone with the sulfonation degree of 45-70 percent and modified nano Al2O3Mixing the/E-CR glass fiber and the aluminum dihydrogen phosphate, uniformly stirring and drying, putting into a double-screw extruder, performing melt extrusion, cooling and demolding, and performing injection molding to obtain the PEEK bar material.
In the step (3), the silane coupling agent is a mixed coupling agent of KH-550 (80%) and KH-602 (20%).
The temperature of each area of the double-screw extruder in the step (4) is as follows: 345 ℃ in the first region, 355 ℃ in the second region, 365 ℃ in the third to fifth regions, 375 ℃ in the sixth to ninth regions, 365 ℃ at the head temperature and the screw rotation speed: 320 rpm.
The bar comprises: sulfonated polyether ether ketone and modified nano Al2O3The mass ratio of the E-CR glass fiber to the aluminum dihydrogen phosphate is 1: 0.2: 0.4.
the modified nano Al2O3the/E-CR glass fiber consists of nano Al2O3/E-CR glassThe glass fiber is prepared by coating with a coupling agent, and the coating mass ratio is 1%.
The nano Al2O3The raw materials of each component of the E-CR glass fiber comprise: the mass ratio of the pretreated E-CR glass fiber to the potassium hexametaphosphate to the aluminum sulfate is 1: 0.03: 0.1.
the pretreated E-CR glass fiber is obtained by acidizing the surface of the E-CR glass fiber.
Example 2
(1) And (3) soaking the E-CR glass fiber in an oxalic acid solution, heating in a water bath at 50 ℃, stirring and ultrasonically treating for 3 hours, cleaning residual acid radical ions on the surface of the E-CR glass fiber by using deionized water after filtering, and drying in a vacuum drying oven to obtain the pretreated E-CR glass fiber.
(2) Adding pretreated E-CR glass fiber and potassium hexametaphosphate into deionized water, stirring and ultrasonically dispersing, adding aluminum sulfate to form a suspension, heating in a water bath to 90 ℃, dropwise adding sulfuric acid and potassium hydroxide solution, adjusting the pH value to 5.5, reacting for 45min, filtering, washing residual sulfate ions on the surface with deionized water, and drying in a vacuum drying oven to obtain the nano Al2O3a/E-CR glass fiber material.
(3) Dispersing silane coupling agent in ethanol, stirring to regulate pH value, adding nano Al2O3Performing ultrasonic dispersion on the/E-CR glass fiber for 45min, performing reflux reaction for 8h at the temperature of 80 ℃, filtering, cleaning and drying to obtain the modified nano Al2O3E-CR glass fibers;
(4) 30g of sulfonated polyether ether ketone with the sulfonation degree of 45-70 percent and modified nano Al2O3Mixing the/E-CR glass fiber and aluminum dihydrogen phosphate, uniformly stirring and drying, putting into a double-screw extruder, performing melt extrusion, cooling and demolding, and performing injection molding to obtain the PEEK bar.
In the step (3), the silane coupling agent is a mixed coupling agent of KH-550 (85%) and KH-602 (15%).
The temperature of each area of the double-screw extruder in the step (4) is as follows: 350 ℃ in the first area, 360 ℃ in the second area, 370 ℃ in the third area to the fifth area, 380 ℃ in the sixth area to the ninth area, 370 ℃ in the head temperature, and the screw rotation speed: 350 rpm.
The bar comprises: sulfonated polyether ethersKetone, modified nano Al2O3The mass ratio of the E-CR glass fiber to the aluminum dihydrogen phosphate is 1: 0.25: 0.5.
the modified nano Al2O3the/E-CR glass fiber consists of nano Al2O3the/E-CR glass fiber is prepared by coating a coupling agent, and the coating mass ratio is 1.5%.
The nano Al2O3The raw materials of each component of the E-CR glass fiber comprise: the mass ratio of the pretreated E-CR glass fiber to the potassium hexametaphosphate to the aluminum sulfate is 1: 0.04: 0.2.
the pretreated E-CR glass fiber is obtained by acidizing the surface of the E-CR glass fiber.
Example 3
(1) And (3) soaking the E-CR glass fiber in an oxalic acid solution, heating in a water bath at 60 ℃, stirring and ultrasonically treating for 4 hours, cleaning residual acid radical ions on the surface of the E-CR glass fiber by using deionized water after filtering, and drying in a vacuum drying oven to obtain the pretreated E-CR glass fiber.
(2) Adding pretreated E-CR glass fiber and potassium hexametaphosphate into deionized water, stirring and ultrasonically dispersing, adding aluminum sulfate to form a suspension, heating in a water bath to 120 ℃, dropwise adding sulfuric acid and potassium hydroxide solution, adjusting the pH value to 6, reacting for 1h, filtering, washing residual sulfate ions on the surface with deionized water, and drying in a vacuum drying oven to obtain the nano Al2O3a/E-CR glass fiber material.
(3) Dispersing silane coupling agent in ethanol, stirring to regulate pH value, adding nano Al2O3Performing ultrasonic dispersion on the/E-CR glass fiber for 1h, performing reflux reaction for 10h at the temperature of 85 ℃, filtering, cleaning and drying to obtain the modified nano Al2O3E-CR glass fibers;
(4) 30g of sulfonated polyether ether ketone with the sulfonation degree of 45-70 percent and modified nano Al2O3Mixing the E-CR glass fiber and the dihydrogen phosphate, uniformly stirring and drying, putting into a double-screw extruder, performing melt extrusion, cooling and demolding, and performing injection molding to obtain the PEEK bar material.
In the step (3), the silane coupling agent is a mixed coupling agent of KH-550 (90%) and KH-602 (10%).
The temperature of each area of the double-screw extruder in the step (4) is as follows: 355 ℃ in the first area, 365 ℃ in the second area, 375 ℃ in the third area to the fifth area, 385 ℃ in the sixth area to the ninth area, 375 ℃ at the head and the screw rotation speed: 370 rpm.
The bar comprises: sulfonated polyether ether ketone and modified nano Al2O3The mass ratio of the E-CR glass fiber to the aluminum dihydrogen phosphate is 1: 0.3: 0.6.
the modified nano Al2O3the/E-CR glass fiber consists of nano Al2O3the/E-CR glass fiber is prepared by coating a coupling agent, and the coating mass ratio is 2%.
The nano Al2O3The raw materials of each component of the E-CR glass fiber comprise: the mass ratio of the pretreated E-CR glass fiber to the potassium hexametaphosphate to the aluminum sulfate is 1: 0.05: 0.3.
the pretreated E-CR glass fiber is obtained by acidizing the surface of the E-CR glass fiber.
Comparative example 1
Comparative example 1 no aluminium dihydrogen phosphate filler was added in step (4) and the other process conditions were identical to those of example 1.
(1) And (3) soaking the E-CR glass fiber in an oxalic acid solution, heating in a water bath at 40 ℃, stirring and ultrasonically treating for 2 hours, cleaning residual acid radical ions on the surface of the E-CR glass fiber with deionized water after filtering, and drying in a vacuum drying oven to obtain the pretreated E-CR glass fiber.
(2) Adding pretreated E-CR glass fiber and potassium hexametaphosphate into deionized water, stirring and ultrasonically dispersing, adding aluminum sulfate to form a suspension, heating in a water bath to 70 ℃, dropwise adding sulfuric acid and potassium hydroxide solution, adjusting the pH value to 4.5, reacting for 0.5h, filtering, washing residual sulfate ions on the surface with deionized water, and drying in a vacuum drying oven to obtain the nano Al2O3a/E-CR glass fiber material.
(3) Dispersing silane coupling agent in ethanol, stirring to regulate pH value, adding nano Al2O3Performing ultrasonic dispersion on the/E-CR glass fiber for 0.5h, performing reflux reaction for 6h at the temperature of 75 ℃, filtering, cleaning and drying to obtain the modified nano Al2O3E-CR glass fibers;
(4) will sulfonate30g of sulfonated polyether ether ketone with the degree of 45-70 percent and modified nano Al2O3Mixing the/E-CR glass fibers, uniformly stirring and drying, putting into a double-screw extruder, performing melt extrusion, cooling and demolding, and performing injection molding to obtain the PEEK bar material.
In the step (3), the silane coupling agent is a mixed coupling agent of KH-550 (80%) and KH-602 (20%).
The temperature of each area of the double-screw extruder in the step (4) is as follows: 345 ℃ in the first region, 355 ℃ in the second region, 365 ℃ in the third to fifth regions, 375 ℃ in the sixth to ninth regions, 365 ℃ at the head temperature and the screw rotation speed: 320 rpm.
The bar comprises: sulfonated polyether ether ketone and modified nano Al2O3The mass ratio of the E-CR glass fiber is 1: 0.2.
the modified nano Al2O3the/E-CR glass fiber consists of nano Al2O3the/E-CR glass fiber is prepared by coating a coupling agent, and the coating mass ratio is 1%.
The nano Al2O3The raw materials of each component of the E-CR glass fiber comprise: the mass ratio of the pretreated E-CR glass fiber to the potassium hexametaphosphate to the aluminum sulfate is 1: 0.03: 0.1.
the pretreated E-CR glass fiber is obtained by acidizing the surface of the E-CR glass fiber.
Comparative example 2
The comparative example 2 and the example 2 reduce the nano alumina coating process, and other processes are consistent with the example 2.
(1) And (3) soaking the E-CR glass fiber in an oxalic acid solution, heating in a water bath at 50 ℃, stirring and ultrasonically treating for 3 hours, cleaning residual acid radical ions on the surface of the E-CR glass fiber by using deionized water after filtering, and drying in a vacuum drying oven to obtain the pretreated E-CR glass fiber.
(2) Dispersing a silane coupling agent in ethanol, stirring to adjust the pH value, adding pretreated E-CR glass fiber, performing ultrasonic dispersion for 45min, performing reflux reaction at 80 ℃ for 8h, filtering, cleaning and drying to obtain the modified E-CR glass fiber.
(3) 30g of sulfonated polyether ether ketone with the sulfonation degree of 45-70%, 30g of modified E-CR glass fiber and aluminum dihydrogen phosphate are mixed, uniformly stirred and dried, and then the mixture is put into a double-screw extruder to be subjected to melt extrusion, cooling demolding and injection molding to obtain the PEEK bar.
In the step (3), the silane coupling agent is a mixed coupling agent of KH-550 (85%) and KH-602 (15%).
The temperature of each area of the double-screw extruder in the step (4) is as follows: 350 ℃ in the first area, 360 ℃ in the second area, 370 ℃ in the third area to the fifth area, 380 ℃ in the sixth area to the ninth area, 370 ℃ in the head temperature, and the screw rotation speed: 350 rpm.
The bar comprises: the mass ratio of the sulfonated polyether ether ketone to the modified E-CR glass fiber to the aluminum dihydrogen phosphate is 1: 0.25: 0.5.
the modified E-CR glass fiber is prepared by coating a pretreated E-CR glass fiber with a coupling agent, and the coating mass ratio is 1.5%.
The pretreated E-CR glass fiber is obtained by acidizing the surface of the E-CR glass fiber.
Comparative example 3
Comparative example 3 the silane coupling agent in step (3) was KH-550, and the other process conditions were the same as in example 3.
(1) And (3) soaking the E-CR glass fiber in an oxalic acid solution, heating in a water bath at 60 ℃, stirring and ultrasonically treating for 4 hours, cleaning residual acid radical ions on the surface of the E-CR glass fiber by using deionized water after filtering, and drying in a vacuum drying oven to obtain the pretreated E-CR glass fiber.
(2) Adding pretreated E-CR glass fiber and potassium hexametaphosphate into deionized water, stirring and ultrasonically dispersing, adding aluminum sulfate to form a suspension, heating in a water bath to 120 ℃, dropwise adding sulfuric acid and potassium hydroxide solution, adjusting the pH value to 6, reacting for 1h, filtering, washing residual sulfate ions on the surface with deionized water, and drying in a vacuum drying oven to obtain the nano Al2O3a/E-CR glass fiber material.
(3) Dispersing silane coupling agent in ethanol, stirring to regulate pH value, adding nano Al2O3Performing ultrasonic dispersion on the/E-CR glass fiber for 1h, performing reflux reaction for 10h at the temperature of 85 ℃, filtering, cleaning and drying to obtain the modified nano Al2O3E-CR glass fibers;
(4) 30g of sulfonated polyether ether ketone with the sulfonation degree of 45-70 percent and modified nano Al2O3Putting the/E-CR glass fiber and the aluminum dihydrogen phosphate into a reaction vessel, uniformly stirring and drying, putting into a double-screw extruder, performing melt extrusion, cooling and demolding, and performing injection molding to obtain the PEEK bar material.
In the step (3), the silane coupling agent is KH 550.
The temperature of each area of the double-screw extruder in the step (4) is as follows: 355 ℃ in the first area, 365 ℃ in the second area, 375 ℃ in the third area to the fifth area, 385 ℃ in the sixth area to the ninth area, 375 ℃ at the head and the screw rotation speed: 370 rpm.
The bar comprises: sulfonated polyether ether ketone and modified nano Al2O3The mass ratio of the E-CR glass fiber to the aluminum dihydrogen phosphate is 1: 0.3: 0.6.
the modified nano Al2O3the/E-CR glass fiber consists of nano Al2O3the/E-CR glass fiber is prepared by coating a coupling agent, and the coating mass ratio is 2%.
The nano Al2O3The raw materials of each component of the E-CR glass fiber comprise: the mass ratio of the pretreated E-CR glass fiber to the potassium hexametaphosphate to the aluminum sulfate is 1: 0.05: 0.3.
the pretreated E-CR glass fiber is obtained by acidizing the surface of the E-CR glass fiber.
Comparative example 4
Comparative example 4 the silane coupling agent in step (3) was KH-602 and the other process conditions were the same as in example 3.
(1) And (3) soaking the E-CR glass fiber in an oxalic acid solution, heating in a water bath at 60 ℃, stirring and ultrasonically treating for 4 hours, cleaning residual acid radical ions on the surface of the E-CR glass fiber by using deionized water after filtering, and drying in a vacuum drying oven to obtain the pretreated E-CR glass fiber.
(2) Adding pretreated E-CR glass fiber and potassium hexametaphosphate into deionized water, stirring and ultrasonically dispersing, adding aluminum sulfate to form a suspension, heating in a water bath to 120 ℃, dropwise adding sulfuric acid and potassium hydroxide solution, adjusting the pH value to 6, reacting for 1h, filtering, washing residual sulfate ions on the surface with deionized water, and drying in a vacuum drying oven to obtain the nano Al2O3a/E-CR glass fiber material.
(3) Will be provided withDispersing silane coupling agent in ethanol, stirring to regulate pH value, adding nano Al2O3Performing ultrasonic dispersion on the/E-CR glass fiber for 1h, performing reflux reaction for 10h at the temperature of 85 ℃, filtering, cleaning and drying to obtain the modified nano Al2O3E-CR glass fibers;
(4) 30g of sulfonated polyether ether ketone with the sulfonation degree of 45-70 percent and modified nano Al2O3Putting the/E-CR glass fiber and the aluminum dihydrogen phosphate into a reaction vessel, uniformly stirring and drying, putting into a double-screw extruder, performing melt extrusion, cooling and demolding, and performing injection molding to obtain the PEEK bar material.
In the step (3), the silane coupling agent is KH 602.
The temperature of each area of the double-screw extruder in the step (4) is as follows: 355 ℃ in the first area, 365 ℃ in the second area, 375 ℃ in the third area to the fifth area, 385 ℃ in the sixth area to the ninth area, 375 ℃ at the head and the screw rotation speed: 370 rpm.
The bar comprises: sulfonated polyether ether ketone and modified nano Al2O3The mass ratio of the E-CR glass fiber to the aluminum dihydrogen phosphate is 1: 0.3: 0.6.
the modified nano Al2O3the/E-CR glass fiber consists of nano Al2O3the/E-CR glass fiber is prepared by coating a coupling agent, and the coating mass ratio is 2%.
The nano Al2O3The raw materials of each component of the E-CR glass fiber comprise: the mass ratio of the pretreated E-CR glass fiber to the potassium hexametaphosphate to the aluminum sulfate is 1: 0.05: 0.3.
the pretreated E-CR glass fiber is obtained by acidizing the surface of the E-CR glass fiber.
Experiment 1:
DSC tests were performed on examples 1 to 3, comparative examples 1 to 4, and commercially available PEEK resin samples that were melt kneaded, and the glass transition temperatures of the respective samples were measured as shown in Table 1 below:
TABLE 1
As can be seen from Table 1, the modified polyetheretherketone/nano-Al of the present invention2O3Compared with PEEK resin, the glass-transition temperature of the E-CR glass fiber composite bar is obviously improved, and various performances of the PEEK resin are deteriorated after the use temperature of the PEEK resin exceeds the glass-transition temperature, so that the thermal performance of the PEEK resin is improved after the PEEK resin is modified; the sample of comparative example 1 is not added with aluminum dihydrogen phosphate filler, other process conditions are the same as those of example 1, and the glass transition temperature of comparative example 1 is lower than that of example 1, which shows that the thermal property of the polyether-ether-ketone modified by phosphate can be improved; compared with the example 2, the coating process of the nano alumina is reduced, other processes are consistent with those of the example 2, the glass transition temperature of the comparative example 2 is not much different from that of the example 2, and the modification of the polyether-ether-ketone by the alumina in the E-CR glass fiber can improve the thermal property of the E-CR glass fiber; compared with the example 3, the comparative examples 3 and 4 show that the glass transition temperature of the material is increased by using a single coupling agent in the comparative examples 3 and 4, which is probably the synergistic effect of the two coupling agents, compared with the material obtained by using the mixed coupling agent in the example 3, and the interfacial bonding performance of the inorganic phase and the organic resin is improved, so that the good modification effect of the inorganic substance on the polyether-ether-ketone is achieved.
Experiment 2:
examples 1 to 3, comparative examples 1 to 4 and commercially available PEEK resin samples were subjected to a frictional property test using a UMT-2 frictional wear tester under a test condition of 25 ℃ at 50rev/min and 5 MPa. The dry coefficient of friction for each sample is shown in table 2 below:
TABLE 2
As can be seen from Table 2, the modified polyetheretherketone/nano-Al of the present invention2O3The friction coefficients of the/E-CR glass fiber composite bar are reduced to different degrees compared with that of PEEK resin, which shows that the wear resistance of the modified material is improved to different degrees; comparative example 1 the vitrification friction coefficient is not much different from that of example 1, which shows that the modification of the polyether-ether-ketone by the phosphate has little influence on the wear resistance; comparative example 2 in comparison with example 2, comparative example 2 in comparison with exampleThe product has a large friction coefficient, but is reduced compared with PEEK resin, which shows that the wear resistance of the product can be improved by taking the nano aluminum oxide as a filler for the PEEK, and the wear resistance of the product can also be improved by E-CR glass fiber or phosphate; compared with the example 3, the comparative examples 3 and 4 show that the friction coefficients of the samples of the comparative examples 3 and 4 are higher than that of the sample of the example 3, and are consistent with the experiment 1, and the use of the mixed coupling agent is more beneficial to improving the interface bonding performance of the inorganic phase and the organic resin, so that the good modification effect of the inorganic substance on the polyether-ether-ketone is achieved.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A processing technology of PEEK bar is characterized in that; the method comprises the following steps:
(1) soaking the E-CR glass fiber in an acid solution, heating, stirring and ultrasonically treating, filtering, cleaning and drying to obtain a pretreated E-CR glass fiber;
(2) adding pretreated E-CR glass fiber and potassium hexametaphosphate into deionized water, stirring and ultrasonically dispersing, adding aluminum sulfate to form suspension, heating in water bath to 70-120 deg.C, dripping sulfuric acid and potassium hydroxide solution, adjusting pH, and reacting for 0.5-1h to obtain nano Al2O3E-CR glass fibers;
(3) dispersing silane coupling agent in ethanol, stirring to regulate pH value, adding nano Al2O3Performing ultrasonic dispersion on the E-CR glass fiber for 0.5 to 1 hour, performing reflux reaction for 6 to 10 hours at the temperature of between 75 and 85 ℃, filtering, cleaning and drying to obtain the modified nano Al2O3E-CR glass fibers;
(4) sulfonated polyether ether ketone and modified nano Al2O3E-CR glassAnd mixing the fibers and the aluminum dihydrogen phosphate, uniformly stirring and drying, putting into a double-screw extruder, performing melt extrusion, cooling and demolding, and performing injection molding to obtain the PEEK bar.
2. The processing technology of PEEK bar material of claim 1, which is characterized in that: the acid solution in the step (1) is one of oxalic acid, pyruvic acid and phosphoric acid.
3. The processing technology of PEEK bar material of claim 1, which is characterized in that: in the step (3), the silane coupling agent is a mixed coupling agent of KH-550 and KH-602.
4. The processing technology of PEEK bar material of claim 1, which is characterized in that: the sulfonation degree of the sulfonated polyether ether ketone in the step (3) is 45-70%.
5. The processing technology of PEEK bar material of claim 1, which is characterized in that: the temperature of each area of the double-screw extruder in the step (4) is as follows: the first zone 345-355 ℃, the second zone 355-365 ℃, the third zone to the fifth zone 365-375 ℃, the sixth zone to the ninth zone 375-385 ℃, the head temperature 365-375 ℃, and the screw rotation speed: 320-.
6. A PEEK rod, characterized in that it comprises: sulfonated polyether ether ketone and modified nano Al2O3The mass ratio of the E-CR glass fiber to the aluminum dihydrogen phosphate is 1: (0.2-0.3): (0.4-0.6).
7. PEEK rod according to claim 6, wherein the modified nano Al is2O3the/E-CR glass fiber consists of nano Al2O3the/E-CR glass fiber is prepared by coating a coupling agent, and the coating mass ratio is (1-2%).
8. PEEK rod according to claim 7, wherein the nano Al is2O3The raw materials of each component of the E-CR glass fiber comprise:the mass ratio of the pretreated E-CR glass fiber to the potassium hexametaphosphate to the aluminum sulfate is 1: (0.03-0.05): (0.1-0.3).
9. A PEEK rod according to claim 8, characterized in that: the pretreated E-CR glass fiber is obtained by acidizing the surface of the E-CR glass fiber.
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| CN104927298A (en) * | 2015-06-30 | 2015-09-23 | 吉林大学 | Polyetheretherketone-base composite, preparing method thereof and application thereof in friction reduction and wear resistance |
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| CN104927298A (en) * | 2015-06-30 | 2015-09-23 | 吉林大学 | Polyetheretherketone-base composite, preparing method thereof and application thereof in friction reduction and wear resistance |
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