西班牙专利ES2554402A2 Thermoset curing through resistive heating of nanocarbons

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专利摘要:
The invention relates to an in situ thermoset curing process. The curing process is based on the formation of a nanocarbon conducting thermoset and resistive heating. Furthermore, the invention relates to process for in situ repairing composites and a process for soldering based on the thermoset curing process through resistive heating.
公开号:ES2554402A2
申请号:ES201590097
申请日:2013-03-19
公开日:2015-12-18
发明作者:Juan José VILATELA GARCÍA；Bartolomé MAS MONSERRAT；Juan Pedro FERNÁNDEZ BLÁZQUEZ；Humprhrey BUNYAN；Jonathan Duval
申请人:Future Fibres Rigging Systems SL；Fund Imdea Mat；FUNDACION IMDEA MATERIALES；Future Fibres Rigging Sys S L；
IPC主号:

专利说明:

Curing of thermosets through resistive heating of nanocarbons
DESCRIPTION
The invention relates to a process of in situ curing of thermosets through resistive heating. In addition, the invention relates to a process for in situ repair of composite materials and a process for in situ welding based on the thermostable curing process through resistive heating.
10
PREVIOUS TECHNIQUE
Curing in polymer chemistry and in process engineering refers to the hardening of a polymeric material by crosslinking of polymer chains, achieved by chemical additives, ultraviolet radiation, electron beam or heat.
A convection oven is generally used to transmit heat, but these furnace technologies are limited to sizes of the pieces that are to be cured smaller than the dimensions of the ovens or autoclaves and still need a long 20 cure times; Therefore, other technologies such as ultraviolet, infrared or microwave ovens or autoclaves are also used. For example, US-2012 / 0.111.497 describes the reduction of curing time - compared to traditional curing with a convection oven - of a thermostable matrix made of epoxy resin and carbon nanotubes (NTC). Since the NTCs have excellent microwave absorption properties, the microwave energy absorbed by the NTCs can be converted into heat energy and the epoxy resin can be cured by means of a microwave oven (MO). However, the temperature of the part during curing is difficult to control since the energy absorption of the part depends on several parameters (for example, volume, volume fraction of the load).
30
Other composite material curing procedures are based on the Joule effect. Interesting examples are those that intentionally incorporate particles
metallic in thermostable insulators in order to make them conductive. Curing is carried out by a current flow directly through the adapted conductive thermosets [GB-2,309,925], however, a large amount of metal particles, approximately 30-95% by weight, and high powers are required. 5 to cure thermosets using the Joule effect mentioned.
On the other hand, the autoclave curing process of carbon fiber (FC) / resin composite materials has basically remained unchanged until the high electrical conductivity of the FCs has been used to produce electrodes. For example, the fibers are first pre-impregnated in thermosets and subsequently cured by Joule effect, passing an electric current through the FC thermostable [Joseph C, Viney C. Electrical resistance curing of carbon-fiber / epoxy composites. Comp. Sci. Tech. 2000; 60: p. 315-319], Curing with electrical resistance heats the composite material directly, and significantly less energy is used compared to oven curing. However, this technique still requires heat transfer over large distances (tens of micrometers) in the thermostable, which is inconvenient since thermosets are very poor thermal conductors. This situation gives rise, for example, to thermal gradients in the sample that produce a non-uniform cure.
twenty
For the reasons stated above, it is necessary to develop a more efficient thermostable curing process in terms of energy that can provide rapid heating rates while producing a uniform curing of the parts, without requiring the addition of large amounts of agents ( > 1% by weight) that 25 may compromise other properties.
SUMMARY OF THE INVENTION
Nanocarbons, such as, for example, carbon and graphene nanotubes, have a unique combination of mechanical, electrical and thermal properties parallel to the plane of the graffiti layers, combined with a very high specific surface area and height-width ratio (area ratio / thickness for graphene). One of the ways to take advantage
These properties on a macroscopic scale consist of dispersing them in a polymer matrix. Normally, the low-volume fractions of the nanocarbons produce the improvement of the matrix properties and / or the addition of new functionalities to the matrix. For example, an electric percolation with less than 0.1% by volume of nanocarbons can often be achieved to reach values in the range of 0.1-1.0 S / m of electrical conductivity.
A first aspect of the present invention relates to a process for in situ curing of thermosets comprising the following steps:
10
a) formation of a nanocarbon conductive thermostable by incorporating 0.001-0.5% by weight of nanocarbons into a thermostable matrix, or by incorporating at least 5% by weight of a thermostable into a nanocarbon matrix, being these percentages by weight with respect to the final weight of the
15 thermoset nanocarbon conductor,
b) optional incorporation of at least one additive to the thermostable obtained in step (a),
c) electric power supply of a value between 1 mW and 100 kW at 20 thermostable stage (a) or (b) to raise its temperature to a temperature value
between room temperature and 400 ° C using a heating rate of between 0.01 ° C / min and 1,000 ° C / min and maintaining the temperature for at least 5 minutes, and
d) supply of electrical energy of a value between 1 mW to 100 kW to the thermostable stage 25 (c) to raise its temperature to a temperature value between
ambient temperature and 400 ° C using a heating rate between 1 and 780 ° C / min and maintaining the temperature for at least 5 minutes,
in which steps (c) and (d) are performed by detecting the actual temperature of the nanocarbon conductive thermostable 30 and adjusting the current flowing through the nanocarbon conductive thermostable depending on the actual temperature detected.
The comparison between the resistive heating of the present invention and the oven processes in terms of the power required for curing will depend on the specific characteristics of the oven and the mold, among others, but the resistive heating is by definition more efficient since it converts all electricity in heat, 5 while the oven has thermal losses when it transfers heat from its elements to the sample mold. As a reference, the present invention requires less than 5 kJ to cure a sample of approximately 1 cm3, compared to the 3 MJ used with a standard laboratory oven (with capacity to cure approximately 100 pieces of that size).
10
Curing through resistive heating has the additional advantage that it allows rapid adjustment of the sample temperature and the power that is supplied in comparison to oven procedures. For example, once the exothermic curing reaction begins, the electrical energy can be reduced accordingly to take advantage of the energy released by the sample, a procedure that would be more complex in an oven due to its high thermal mass.
In addition, cooling rates after curing are also noticeably faster when resistive heating is used, since it is primarily the sample 20 that must reach room temperature, while in the oven procedure after removing the sample from the oven both The sample as the mold should be cooled.
In a preferred embodiment, the thermostable of step (a) is selected from list 25 consisting of epoxy resins or phenolic resins, polyesters, polyurethanes, polyamides, acrylates, elastomeric materials, rubbers, silicones and a combination thereof.
In a more preferred embodiment, the thermostable is an epoxy resin or a phenolic resin.
In another preferred embodiment, the nanocarbons of step (a) are selected from the

list consisting of carbon nanotubes (NTC), graphene, graphene oxide, carbon filaments, macroscopic fibers made of NTC or graphene, NTC films, graphene films and a combination thereof.
5 The term "graphene" as used herein also refers to reduced graphene oxide, monolayer and multilayer graphene and high purity graphene obtained by chemical vapor deposition, among others.
The term "carbon filaments" also known as carbon fibers obtained in steam, carbon nanofibers and graphite filaments, refers to graffiti fibers with a diameter normally within the range 15 nm-500 nm.
In another preferred embodiment, the formation of the nanocarbon conductive thermostable of step (a) is carried out by incorporating 0.001-0.1% by weight of 15 nanocarbons into a thermostable matrix.
In another preferred embodiment, the formation of the nanocarbon conductive thermostable of step (a) is carried out by incorporating 5-50% by weight of a thermostable into a nanocarbon matrix.
twenty
In a preferred embodiment of step (a), the incorporation of nanocarbons into a thermostable matrix is carried out by means of uniform dispersion techniques, such as milling, calendering, sonication and centrifugation.
25 Thermosets are electrical insulators. The addition of nanocarbons in low proportions (0.001-0.5% by weight) provides a certain electrical conductivity that allows resistive heating when electric current passes through them while they are integrated into the thermostable.
30 An advantage of incorporating nanocarbons into a thermostable matrix is the achievement of resistive heat conduction in the material itself. On the other hand, in oven procedures, heat must be transferred from the resistive elements to the mold and from the
Sample mold. Even for low NTC volume fractions of nanocarbons, the separation between NTC is less than 100 nm, which implies that the distance between heat sources is also less than 100 nm. This distance corresponds approximately to the distance in which the heat circulates in the thermostable of low conduction capacity; Thus, it is desirable to make it as small as possible.
The uniform dispersion of the nanocarbons in a thermosetting matrix achieves a uniform cure and consequently homogeneous properties of the cured composite material. By measuring the glass transition temperature of samples of similar composite materials produced in similar temperature cycles, it is observed that the samples of resistive cured composite materials vary approximately 1% in their glass transition temperature while those cured in the oven vary a 15% across the sample.
In another preferred embodiment of step (a), the incorporation of a thermostable in a nanocarbon matrix is carried out by means of infusion, injection, bathing, impregnation, resin transfer molding, vacuum assisted resin transfer molding, impregnation and combinations of these techniques.
Step (b) of the process for in situ curing of thermosets refers to the incorporation of at least one additive to the thermostable obtained in step (a). This stage (b) is optional.
In a preferred embodiment of step (b), the additives are selected from the list consisting of reinforcing elements, catalysts, antioxidants, UV stabilizers and flame retardants.
The catalysts will be selected from the list consisting of dimethylamine, monoethylamine, triamines, aminomethylphenol and a combination thereof.
30
The reinforcing elements will be selected from the list consisting of macroscopic fibers, glass fibers, short fibers, carbon fibers, polymeric fibers, fibers
natural and a combination thereof.
Antioxidants will be selected from the list consisting of aromatic amines and phenols with steric hindrance.
5
UV stabilizers will be selected from the list consisting of oxanilides, benzophenones, benzotriazoles, hydroxyphenyltriacines and a combination thereof.
The flame retardants will be selected from the list containing phosphates, 10 or boric phosphoric acid, borates, sulfates, aluminum or magnesium hydroxides, magnesium carbonates, hydromagnesite and a combination thereof. In a more preferred embodiment, phosphates are selected from the list consisting of monoammonium phosphate, diamonium phosphate, melanin phosphate and a combination thereof.
15 Stage (c) of the thermostable curing process in situ refers to the supply of electrical energy of a value between 1 mW and 100 kW to the thermostable stage (a) or (b) in order to raise its temperature at a temperature value between room temperature and 400 ° C using a heating rate between 0.01 ° C / min and 1,000 ° C / min and maintaining the temperature for at least 5 minutes by means of the detection of the actual temperature of the thermostable conductor of nanocarbons and adjusting the current flowing through the thermostable conductor of nanocarbons depending on the actual temperature detected.
In a preferred embodiment of step (c), the electrical energy supplied to the thermostable is between 1 W and 1 kW.
In another preferred embodiment of step (c), the temperature of the thermostable reached by supplying electric power has a value between 50 and 200 ° C.
In another preferred embodiment of step (c), the heating rate is between the values 1 ° C / min and 100 ° C / min.
Step (d) of the thermostable curing process in situ refers to the supply of electrical energy of a value between 1 mW and 100 kW to the thermostable stage (c) to raise its temperature to a temperature value between the temperature ambient and 400 ° C using a heating rate between 1 and 5 780 ° C / min and maintaining the temperature for at least 5 minutes, by detecting the actual temperature of the thermostable nanocarbon conductor and adjusting the current flowing to through the thermostable nanocarbon conductor depending on the actual temperature detected.
In a preferred embodiment of step (d), the electrical energy supplied to the thermostable is comprised in a value between 1 W and 1 kW.
In another preferred embodiment of step (d), the temperature of the thermostable reached by supplying electric power has a value between 50 and 200 ° C.
fifteen
In another preferred embodiment of step (d), the heating rate is between the values 1 ° C / min and 100 ° C / min.
Another aspect of the present invention relates to a process for in situ repair of composite materials according to the thermostable curing process of the invention described above, further comprising a step b "), between step b) and the stage c), of placing the thermostable of stage b) in contact with the surface to be repaired.
The term "composite materials" as used herein refers to materials made from two or more constituent materials with significantly different physical or chemical properties, which when combined, produce a material with different characteristics of the components. individual. The individual components remain separate and differentiated within the final structure 30.
A clear advantage of this procedure is the possibility of curing in situ, without having to
Bring the parts that will undergo repair to an oven, particularly for large pieces of composite materials such as aerospace panels.
Another aspect of the present invention relates to a welding process, in accordance with the thermostable curing method of the invention described above, further comprising a stage b '), between stage b) and stage c), for placing the thermostable stage b) in contact with the metal surface.
Traditional welding procedures, for example for metal cables, usually use molten soft metals at temperatures between 200 and 500 ° C. Such procedures may not be suitable for nanocarbon-based materials, firstly because they can cause damage to the materials by oxidation and secondly because molten metals do not normally wet NTC fibers and, therefore, are unlikely to produce Good welding contact without chemical fiber treatment.
Unless otherwise defined, all technical and scientific terms used in the present specification have the same meaning commonly understood by one skilled in the art to which the present invention belongs. Methods and materials similar or equivalent to those described herein may be used in the practice of the present invention. Throughout the description and the claims the word "understand" and its variants are not intended to exclude other technical characteristics, additives, components or steps. The objects, advantages and additional features of the invention will be apparent to those skilled in the art after the study of the description or can be learned with the practice of the invention. The following examples, drawings and sequence listings are offered by way of illustration and are not intended to limit the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
30
Figure 1 Schematic of a configuration used to cure a thermostable containing NTC through resistive heating.
Figure 2 Graph showing that resistive heating can be controlled to follow a predetermined heating protocol. In this case, the actual sample temperature is used as input for a controller that adjusts the electrical energy supplied to the sample and therefore its temperature.
Figure 3 Schematic representation and photographs of a configuration used for curing a fiberglass reinforced composite material.
10 Figure 4 Schematic representation and photographs of a configuration used to repair a panel of aerospace composite material by curing a thermostable through resistive heating.
Figure 5 Procedure for using resistive heating to cure a thermostable 15 in an NTC arrangement to establish an electrical contact between the arrangement and a metal. Ib) shows the porosity of the nanocarbon arrangement that allows the infiltration of epoxy resin into it and therefore makes possible the process of resistive welding of epoxy resin.
20 EXAMPLES
Example 1:
In this example, NTC is added to an epoxy resin in a volume fraction of 25 0.5% by weight and dispersed using an Exakt80E three-roller mill (Exakt Technologies) progressively reducing the distance between rollers. The dispersion is achieved using a constant output roller speed of 250 rpm (the relative speed between rollers is 1: 3: 9) and reducing the distance between them from 125 pma5 pm Once the NTC and resin have dispersed Electrically conductive at 18% 30 by weight, Aradure XB 3473 hardener is added to the mixture.
The hardener was added to the NTC / epoxy resin above and then stirred
mechanically using a Heidolph RZR1 agitator with a TR 21 radial flow impeller.
The addition of NTC to the thermostable makes it electrically conductive, thus making it possible to pass electrical current through it and raise its temperature by means of Joule heating.
As shown in Figure 1, the mixture is placed in a small container with two metal contacts pre-installed at each end connected to a power supply. The sample is heated by passing current through the epoxy resin 10 and the temperature is controlled by modifying the voltage (power) applied between the electrodes, as shown in Figure 2. Thus, in this procedure, the heat source is The sample itself. This implies that when the sample temperature needs to be adjusted, it can be achieved instantly by changing the power supplied to it. In addition, the power can be reduced, for example, to take advantage of the energy released by the exothermic curing reaction. In this example, the power supplied to the 1.5 g sample was approximately 4 W, after verifying various parameters such as mold shape, size, material, room temperature, insulation use, etc.
The uniformity of the sample cured by resistive heating is evaluated by comparing the glass transition temperature of material extracted from the central part of the cured piece with the material of the side edge of the piece (Table 1).
The variation of the glass transition temperature is in a range of 1%. A sample prepared as detailed in this example but cured in the oven under equivalent conditions has a glass transition temperature variation of 15%.
Table 1: Glass transition uniformity in samples cured by resistive heating and standard oven processing.
30
Sample Procedure of Place of Transition Temperature
Cured extracts vitreous (° C)
TO Resistive curing Central part of 95.0
piece
TO Resistive curing Side edge 96
B Resistive curing Central part of 84.3
piece
B Resistive curing Side edge 73
Example 2:
In this example, a thermostable containing NTC prepared as in the previous example is infused into a standard fiberglass arrangement (the diameter of the fibers is between 5 and 50 micrometers) by direct mixing between the two. The structure of the arrangement is normally porous and therefore accessible for infiltration into the thermostable through capillary forces.
10 Figure 3 shows a diagram of the configuration used and photographs illustrating the steps taken during the preparation of the composite material.
Next, the infused arrangement is placed between two flat electrodes consisting of two aluminum plates, connected to a power supply. Then, the sample is heated by passing current through the conductive thermostable so that the sample is cured. Using this resistive curing, heat transfer takes place throughout the sample at the same time. In this example, the power supplied to the sample of ~ 10 g was in the range 15-35 W. It has been chosen taking into account several parameters such as mold shape, size, material, ambient temperature, use insulation, etc.
Scanning electron microscopy images were obtained through EVOMA15 Zeiss SEM. Image Ib) of Figure 5 obtained by scanning electron microscopy shows the cross section of the material that will be cured consistently through it, with no evidence of cracks induced by curing or any sign of heterogeneity, which confirms The total sample volume has been cured.
Example 3: Repair of an aerospace composite panel.
In this example, a fiber reinforced composite composite panel normally used in the aerospace industry is repaired using the composite material prepared as indicated in Example 1 as an adhesive, applying it to the panel to be repaired and curing it by resistive heating. . The configuration used is shown schematically in Figure 4. The repair procedure is shown with photographs also in Figure 4.
10
The starting material is a laminate that was damaged while performing a standard impact test. To repair it in situ, without having to take it to a furnace, a small amount of the composite material prepared as in Example 1 is spread around the damaged area and then covered with a special carbon fiber sheet 15 used for repairs according With the aeronautical specifications. The two parts of composite material, which did not need modification, are used as electrodes and are joined by curing the epoxy resin adhesive by resistive heating by passing current through the part for a few minutes. An electrical contact is established on each panel, for example using conventional silver paint. In this example, the power supplied to the adhesive sample of ~ 3 g was in the range 5-30 W.
The bottom image of Figure 4 shows the repaired composite material that resists a weight of 10 kg.
25
Example 4:
In this example the resistive curing is performed to bond a prepared composite material as described in Example 2 on a metal surface. These composite materials have low density, usually below 1.2 g / cc and can show a very high electrical conductivity of 3 x 106 S / m. These values are comparable to those of copper measured in mass and therefore have great interest for various applications,
and hence the importance of processes such as welding composite materials on a metal substrate to form an electrical contact.
The welding process is shown in Figure 5. Once the prepared composite material 5 is placed as described in Example 2 in contact with the metal surface, a small drop of standard epoxy resin is applied to the composite material. The thermostable ignites instantly in the composite material due to its high internal area, but preserving the electrical contact between the composite material and the metal. Next, a small stream is passed through the sample to cure the composite material. In this example, the power supplied in the sample of ~ 10 mg was approximately 1.5 W. A mechanically robust contact is obtained between the two conductive materials that show a contact resistance value of 2 ohms. For example, a working LED is shown in Figure 5III).
fifteen

权利要求:
Claims (18)
[1]
1. A process for in situ curing of thermosets comprising the following steps:
5
a) formation of a nanocarbon conductive thermostable by incorporating 0.001-0.5% by weight of nanocarbons into a thermostable matrix, or by incorporating at least 5% by weight of a thermostable into a nanocarbon matrix, being these percentages by weight with respect to the final weight of the
10 thermostable nanocarbon conductor,
b) optional incorporation of at least one additive to the thermostable obtained in step (a),
c) electric power supply of a value between 1 mW and 100 kW at 15 thermostable stage (a) or (b) to raise its temperature to a temperature value
between room temperature and 400 ° C using a heating rate between 0.01 ° C / min and 1,000 ° C / min and maintaining the temperature for at least 5 minutes, and
d) supply of electrical energy of a value between 1 mW to 100 kW at 20 thermostable stage (c) to raise its temperature to a temperature value between
ambient temperature and 400 ° C using a heating rate between 1 and 780 ° C / min and maintaining the temperature for at least 5 minutes,
in which steps (c) and (d) are performed by detecting the actual temperature of the nanocarbon conductive thermostable and adjusting the current flowing through the nanocarbon conductive thermostable depending on the actual temperature detected.
[2]
2. The method according to claim 1, wherein the thermostable of step (a) is selected from the list consisting of epoxy resins or resins
Phenolic, polyesters, polyurethanes, polyamides, acrylates, elastomeric materials, rubbers, silicones and a combination thereof.
[3]
3. The method according to claim 2, wherein the thermostable is an epoxy resin or a phenolic resin.
[4]
4. The method according to any one of claims 1 to 3, wherein the nanocarbons of step (a) are selected from the list consisting of
Carbon nanotubes (NTC), graphene, carbon filaments, macroscopic fibers made of NTC or graphene, NTC films, graphene films and a combination thereof.
The method according to any one of claims 1 to 4,
wherein the formation of a nanocarbon conductive thermoset of step (a) is carried out by incorporating 0.001-0.1% by weight of nanocarbons into a thermostable matrix.
The method according to any one of claims 1 to 5,
wherein the formation of a nanocarbon conductive thermoset of step (a) is carried out by incorporating 5-50% by weight of a thermostable into a nanocarbon matrix.
The method according to any one of claims 1 to 6,
wherein the incorporation of nanocarbons into a thermostable matrix of step (a) is carried out by means of uniform dispersion techniques.
[8]
8. The method according to claim 7, wherein the uniform dispersion techniques are selected from the list consisting of grinding, calendering,
sonication and centrifugation.
[9]
9. The method according to any one of claims 1 to 6, wherein the incorporation of a thermostable in a nanocarbon matrix of the stage
30 (a) is performed by means of infusion, injection, bath, impregnation, resin transfer molding, resin assisted vacuum transfer molding, impregnation and combinations of these techniques.
[10]
10. The process according to any one of claims 1 to 9, wherein the additives of step (b) are selected from the list consisting of reinforcing elements, catalysts, antioxidants, UV stabilizers and flame retardants.
5
[11]
11. The method according to claim 10, wherein the reinforcing elements are selected from the list consisting of macroscopic fibers, glass fibers, short fibers, carbon fibers, polymeric fibers, natural fibers and a combination of the same.
10
[12]
12. The method according to claim 10, wherein
Catalysts are selected from the list consisting of dimethylamine, monoethylamine, triamines, aminomethylphenol and a combination thereof.
13. The method according to claim 10, wherein the
Antioxidants are selected from the list consisting of aromatic amines and phenols with steric hindrance.
[14]
14. The method according to claim 10, wherein
20 UV stabilizers are selected from the list consisting of oxanilides,
benzophenones, benzotriazoles, hydroxyphenyltriacines and a combination thereof.
[15]
15. The method according to claim 10, wherein
Fire retardants are selected from the list consisting of phosphates, phosphoric acid or
Boric acid, borates, sulfates, aluminum or magnesium hydroxides, magnesium carbonates, hydromagnesite and a combination thereof.
[16]
16. The process according to claim 15, wherein the phosphates are selected from the list consisting of monoammonium phosphate, diamonium phosphate,
30 melanin phosphate and a combination thereof.
[17]
17. The method according to any one of claims 1 to
16, in which the electrical energy supplied to the thermostable in step (c) is comprised in a value between 1 W and 1 kW.
[18]
18. The method according to any one of claims 1 to 5 17, wherein the temperature of the thermostable reached by supplying electric power
in step (c) it has a value between 50 and 200 ° C.
[19]
19. The method according to any one of claims 1 to
18, in which the heating rate of stage (c) is between 10 values 1 ° C / min and 100 ° C / min.
[20]
20. The method according to any one of claims 1 to
19, in which the electrical energy supplied to the thermostable in step (d) is comprised in a value between 1 W and 1 kW.
fifteen
[21]
21. The method according to any one of claims 1 to
20, in which the temperature of the thermostable reached by supplying electrical energy in step (d) has a value between 50 and 200 ° C.
The method according to any one of claims 1 to
21, in which the heating rate of stage (d) is between the values 1 ° C / min and 100 ° C / min.
[23]
23. A procedure for on-site repair of composite materials, which
25 comprises steps (a) to (d) of the method described in any one of claims 1 to 22, further comprising a stage b "), between stage (a) or (b) and stage (c), placing the thermostable stage (a) or (b) in contact with the surface to be repaired.
30 24. A procedure for spot welding, according to any of the
claims 1 to 22, further comprising a stage b '), between stage b) and stage c), placing the thermostable stage b) in contact with the metal surface.

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同族专利:

公开号 | 公开日

ES2554402R1|2016-02-05|

ES2554402B1|2016-11-15|

引用文献:

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

CN108034240A|2017-12-26|2018-05-15|肖彬|Fiber glass reinforced polyamide material for welding assembly|US7919037B1|2005-01-19|2011-04-05|Darren Boyce|Process and composition for molding heatable articles and resulting product|

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