Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/17—Component parts, details or accessories; Auxiliary operations
  • B29C45/26—Moulds
  • B29C45/37—Mould cavity walls, i.e. the inner surface forming the mould cavity, e.g. linings
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/26—Macromolecular compounds or prepolymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C33/00—Moulds or cores; Details thereof or accessories therefor
  • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/0005—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fibre reinforcements
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
  • B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2964—Artificial fiber or filament

Definitions

• the invention relates to the field of manufacturing by injection or injection-compression of a product or a composite part formed essentially of a thermoplastic organic material reinforced by glass fibers of great length, it is that is, the initial length of the chopped fiberglass is typically between 6 and 30 mm. More specifically, according to the present invention, an injection molding or injection-compression molding process is described, implemented by a device comprising a single-screw and fed with thermoplastic organic material and reinforcing fibers, said fibers being obtained by cutting glass thread for example under die or from roving or roving according to the English term.
• the term matrix designates in the following text said thermoplastic organic material forming part of the finally obtained molded composite material.
• injection refers to all the injection and injection-compression processes and to the term “long fibers" of the fibers as previously described.
• a device comprising a heated cylinder in which an Archimedean screw or a single-screw screw rotates under the action of a motor.
• This cylinder comprises, at the upper part of one of its ends, at least one hopper whose base opens directly on the Archimedes screw. The device is fed with organic matter and glass son through this hopper.
• the organic material in the form of granules and the reinforcing fibers, in the form of cut son, are for example introduced premix in the hopper or in mixture at the hopper by the use of dosers.
• the metering of the cut glass yarns is carried out by metering devices (for example gravimetric) on the basis of a constant flow of materials, the opening times of the feed traps being regulated as a function of the flowability. .
• the dosage of long cut yarns has proved impossible because of the formation of bridges.
• the surface appearance of the injected composite parts is unsatisfactory: Surface appearance problems occur due to the poor dispersion of the long cut yarns. This causes the concentration of the glass fibers on certain parts on the surface of the composite part.
• the single-screw device used during the transformation by the injection process plasticizes the plastic matrix but does not allow, by the low shear generated, a homogeneous dispersion of the glass fibers within the matrix, some of they are neither dispersed in the matrix nor impregnated by the matrix. This poor dispersion at the origin of the surface defects observed is also at the origin of the deterioration of the mechanical characteristics of the composite part obtained by injection (see point c) below). c) The mechanical properties of the composite part obtained are bad:
• thermoplastic composites based on cut glass yarns To avoid these problems, for reinforced thermoplastic composites based on cut glass yarns, a two-step process is currently used:
• thermoplastic matrix a first step using an extruder comprising a twin-screw, resulting in high shear, to allow good dispersion and impregnation of the fiber by the thermoplastic matrix.
• This bi-screw makes it possible to strongly stress the cut son to break the glass filaments by shearing, to allow the impregnation of the fibers thus obtained while ensuring their dispersion within the matrix.
• this high shear exerted also has the effect of greatly reducing the length of the fiber in the matrix, the latter being predominantly less than 1 mm.
• the rods obtained at the outlet of the die are then cut into granules using a granulator.
• these granules obtained are used in a conventional injection device of the single-screw type.
• a conventional injection device of the single-screw type examples of such methods are for example described in patent applications WO 96/40595, WO 98/43920, WO 01/05722 or WO 03/097543.
• Such a process therefore involves two distinct steps, a step of forming a fiber-reinforced granule by extrusion and a step of shaping said granule.
• the first step requires expensive equipment and little widespread, ie an extruder type bi-screw and is most often performed by the formulator (also called compounder in the trade), the second step being performed by the transformer, on the production site of the composite part.
• the present invention thus allows the production of thermoplastic parts reinforced with long fibers, from long cut yarns, while meeting the technical constraints of the process as well as the composite obtained, using only a standard injection device of the mono type. screw. It makes it possible in particular to obtain on the composite part a very satisfactory control of the glass content, a good surface appearance and a good level of mechanical properties.
• the present invention relates to a method of manufacturing a composite part formed by the combination of a thermoplastic matrix reinforced glass fibers of great length, said method comprising an injection molding step or injection-compression , implemented by a device comprising a single-screw fed by said material and said reinforcement, said method being characterized in that the reinforcement fibers are introduced into said device in the form of long cut son granules whose density or glass rate is included between 90 and 99.5%, preferably between 95 and 99% and whose L / D ratio is less than L, expressed in mm.
• the L / D ratio is less than 30 for a granule of length L equal to 30 mm, to 24 for a granule of 24 mm, to 12 for a granule of 12 mm.
• the L / D ratio is less than 2/3 of L, expressed in mm.
• the ratio is less than 20 for a 30 mm long granule, 16 for a 24 mm granule and 8 for a 12 mm granule.
• the L / D ratio is between L / 4 and L / 2, L expressed in mm, for example the L / D ratio is between 7.5 and 15 for a granule of length 30 mm. between 6 and 12 for a granule of 24 mm and between 3 and 6 for a granule of 12 mm.
• the diameter D to be considered for the application of the present process is equal to the smallest measured value of said section.
• the high-density glass granules according to the invention are, for example, synthesized according to the principles, processes and apparatus described in the patent applications WO 96/40595, WO 98/43920, WO 01/05722 or WO 03/097543 to which one applies. refer for the implementation of said synthesis.
• the glass wires used in the context of the invention are generally manufactured according to the following succession of steps:
• the cut threads are wet. They generally comprise from 5 to 25% by weight of water, Example 5 to 15% by weight of water.
• this step it is unnecessary to dry them before introducing them into a brewing step known in either of the aforementioned documents, this step to be carried out in the presence of water and optionally in the presence of a tackifier.
• the possible additional water (with respect to the water supplied by the fiberizing step) necessary for the obtaining a total water content ranging from 10 to 25% by weight of the mass introduced into the brewing apparatus. It is possible and preferable not to have to add additional water (reduction of granulator fouling and increase in yield). For that, it suffices to fiber to a sufficient humidity to obtain a correct granulation.
• the stirring is carried out for a sufficient time so that the increase in the density of the cut son is substantial and this by a brewing apparatus providing at each instant the same brewing frequency son or granules formation it contains the granules finally formed containing, for example, after drying at least 95%, preferably at least 97% and very preferably at least 99% by weight of glass, the optional tackifier being in contact with the glass fibers at most late during brewing.
• the ingredients of the mixture to be stirred are introduced into the stirring apparatus. We thus introduce - the cut sized threads,
• the tackifier can thus be chosen from the compounds cited in application WO 03/097543 such as
• epoxy polymer for example polymer bis-phenol di-glycidyl ether A
• the tackifier may be chosen from EVA (Ethylene Vinyl Acetate) and EEA (Ethylene Acrylic Acid), as described in the following description.
• the tackifier is generally chosen depending on the nature of the thermoplastic to be reinforced.
• the cut son agglomerate by juxtaposing during brewing to form the granules, without changing their length.
• the granules are substantially in the form of cylinders of length substantially identical to that of the longest son introduced at the start. Cut threads having a length ranging from 6 to 30 mm, for example from 8 to 24 mm and typically from 9 to 15 mm and more particularly with an average length of approximately 9 mm, 12 mm or 15 mm, may be used.
• the starting cut yarns may also comprise fines, since these fines participate in the granulation by agglomerating to insert into the granules.
• the filaments contained in the threads may have a diameter ranging for example from 5 to 24 ⁇ m.
• the stirring is carried out for the time sufficient to obtain the desired length / diameter ratio of the granule and / or the desired density increase.
• the density of the granules prepared is generally ⁇
• the high-density glass granule according to the invention generally has a loss on ignition strictly less than 2.0% and even less than 1.5%, for example ranging from 0.5% to 1.5%, in particular ranging from 0.7 to 1.2%.
• An example of a final granulate according to the invention comprises a multitude of parallel glass filaments with a unit diameter ranging from 5 to 24 ⁇ m, these filaments all having the same nominal diameter or having different nominal diameters.
• the number of filaments contained in a granule may especially range from 1,000 to 100,000 depending on the diameter of the filaments, for example 2,000 to 50,000.
• the stack of filaments in the granules is most often of a compact nature.
• the thermoplastic matrix may be chosen from the group consisting of polypropylenes (PP), polyamides (PA), polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), styrenics such as acrylonitrile-butadiene-styrene (ABS), polyethylene (PE), phenylene polysulfide, polyphenylene sulphide (PPS), polycarbonate (PC), polyacetals such as polyethylene oxide (POM).
• PP polypropylenes
• PA polyamides
• PET polyethylene terephthalate
• PBT polybutylene terephthalate
• ABS styrenics
• ABS acrylonitrile-butadiene-styrene
• PE polyethylene
• PPS polyphenylene polysulfide
• PPS polyphenylene sulphide
• PC polycarbonate
• POM polyacetals
• POM polyethylene oxide
• the previous manufacturing process could be further improved by using a sizing whose melting temperature is lower than that of the thermoplastic matrix.
• the difference of said melting temperatures is as high as possible and advantageously greater than 5 ° C., more preferably greater than 70 ° C., very preferably greater than 1O 0 C or 20O 0 C or even 25 0 C.
• melting temperature it is understood in the sense of the description the temperature at which at least 50% by weight, preferably at least 70% by weight and very preferably at least 90% by weight of the dry extract of the size is in molten form.
• a lubricating liquid suitable for the manufacture of long glass fiber high-density granules makes it possible to obtain all of the features presented above, comprises:
• an aqueous emulsion of EVA Ethylene Vinyl Acetate
• EVA Ethylene Vinyl Acetate
• EAA aqueous emulsion of EAA
• PP-MAHg aqueous maleic anhydride grafted polypropylene emulsion
• a stabilizer of the formulation such as N-butylamine (which evaporates during drying )
• an aqueous emulsion of a film-forming polymer such as a polyurethane (PU), process aid additives such as surfactants and / or lubricants and / or
• Rate (% weight of the preferred rate (% dry matter weight) of the dry matter)
• Typical formulations of sizes are, for example, as a percentage of solid material (dry):
• Silane Silquest A1100® (GE), AMEO® (Degussa)
• EVA EVAX28® (Michelman)
• EAA Michem Prime 4983® (Michelman)
• AC5120® ammonium knows in water (Honeywell)
• PP-MAHg Michem 43040® (Michelman), Novacer 1800® (BYK Cera)
• the melting temperature thereof is, according to the invention, between 155 and 120 ° C., that is to say at least 70 ° C. lower. to that of the PP matrix.
• the invention is characterized in that a single-screw device provides the steps of mixing the initial constituents of the part, ie the matrix and the fibers and molding.
• control of the glass content and the dispersion of the fibers in the composite parts injected in such a process are improved by:
• the finally obtained composite product further has improved mechanical properties as can be seen in the following examples.
• FIG. 1 illustrates an exemplary embodiment of an injection method according to the invention.
• Granules made of thermoplastic resin, for example polypropylene and high-density glass granules, that is to say of which, for example, the level of glass is greater than 95%, are introduced in the form of a mixture 8 into a hopper.
• a pneumatic conveyance (not shown in FIG. 1) makes it possible to convey the high-density glass granules to the hopper 2.
• the device 1 in addition to the hopper 2, comprises a monovis 3 arranged in a sleeve 4 whose walls are heated. by annular resistors 5, typically at a temperature between 200 and 300 ° C.
• the respective proportions of the two types of granules are adjusted upstream according to known techniques, for example by means of gravimetric metering devices. Under the combined effect of the heat generated by the heating resistors
• the thermoplastic resin granules are plasticized and the melting of the size induces a homogeneous dispersion of the fibers in the thermoplastic matrix.
• the single-screw satisfies two functions according to the present method: a function of plasticizing the thermoplastic material, by turning and retreating,
• thermoplastic resin granules and the high-density glass granules could be injected at different points of the device. Most generally, any known injection molding device can be used for carrying out the present method.
• PU polyurethane
• the ethoxy groups of the silane are hydrolyzed in demineralized water kept stirring, and the other constituents are then added, still with stirring.
• the weight content of solids in the sizing composition is equal to 10%.
• the sized yarns are obtained as follows:
• the sizing compositions are used to coat, in known manner, glass filaments E about 17 ⁇ m in diameter drawn from glass threads flowing out of the orifices of a die which are gathered together into 500 filament yarns. each.
• the yarns obtained after the fiberizing and sizing steps were cut to obtain long cut yarns of average length 12 mm ⁇ 1 mm, of flat shape, that is to say on average 2 mm wide and 0.5 mm thick.
• the measured density of such cut son is 0.40 g / cm 3 .
• the sizing liquid used to gather the filaments into fibers after fiberizing contains the following constituents in percentage of dry matter: - 70% by weight of an aqueous emulsion of EVA (Ethylene Vinyl Acetate), marketed by MICHELMAN under the reference EVAX28 ®, whose weight content of ethylene is 82% and the melting point of the order of HO 0 C,
• EVA Ethylene Vinyl Acetate
• the sizing composition is obtained in a manner similar to that described in Example 1.
• the melting temperature of the size (dry extract) thus obtained begins at a temperature of approximately 120 ° C. and continues to approximately 150 ° C.
• the yarns are obtained and sized similarly to that described in Example 1.
• the son obtained were then cut according to known techniques to obtain long cut son of average length 12 mm ⁇ 1 mm, flat shape (about 2 mm wide and 0.2 mm thick) and density 0.40 g / cm 3 .
• High density glass granules with an average length of 12 mm ⁇ 1 mm, of substantially cylindrical shape and with a mean diameter of 2.5 mm and a density of 0.80 g / cm 3 were obtained by densification of the long cut wires. obtained in Example 2 using the method and a stirring device described in WO 03/097543, to obtain a granule whose glass density is close to 99%.
• the fire loss of the granule, measured according to conventional techniques is less than 1%.
• Thermoplastic granules comprising 30% by weight of glass fibers cut to 12 mm ⁇ 1 mm dispersed in a PP matrix, having a diameter of about 2.5 mm and a density equal to 0.70 g / cm 3 were used. These granules are marketed under the reference Celstran® by TICONA. The granules are prepared according to techniques well known by impregnation of a glass roving by the polypropylene matrix, the weight percentage of said matrix being 70%.
• high-density glass granules of average length equal to 12 mm ⁇ 1 mm, of substantially cylindrical shape and of average diameter 2.5 mm for a density of 0.83 g / cm 3 were obtained by densification of the long cut son obtained in Example 1, to obtain a granule whose glass density is close to 99%.
• the fire loss of the granule, measured according to conventional techniques is less than 1%.
• a flow test of the granules or fibers obtained according to Examples 1 to 5 was carried out. This test makes it possible to evaluate the ability of the chopped strands or granules to flow under specified conditions. This ability is expressed in seconds.
• the measurement of the flow time is carried out on a quantity of products of 5kg.
• the product is placed in a hopper whose discharge space or chute is located at 28.5 mm from a vibrating flow corridor with an amplitude of 1 mm.
• Table 2 summarizes the results obtained in this flow test for each of the products.
• fines means free glass rods or filaments dissociated from the initial product during its transport.
• fines rate the amount of fines collected under the following conditions on a sample of 500 grams of product in a trap, by suction.
• the product to be tested is placed in a hopper, whose outlet chute is located 4 mm from a vibrating corridor allowing flow and homogeneous spreading of the product.
• a suction system with the fine trap is located above this vibrating corridor to capture all free glass rods or filaments.
• the level of fines is expressed in Table 3 in mg / kg. A value equal to or less than 50 is considered satisfactory. 2. Pneumatic transport test (transport test)
• This test consists in simulating a pneumatic transport of cut threads or granules, from a storage area to a feed hopper of an injection molding machine of the type described with reference to FIG. 1, for example.
• Two kilograms of the product to be tested (chopped strands or granules) are placed in a storage tank, then sucked by a pneumatic injection hopper of conventional technology, causing the product to pass along a critical circuit. say favoring the formation of fibrils or flock of filaments of glass wire.
• a pneumatic injection hopper of conventional technology say favoring the formation of fibrils or flock of filaments of glass wire.
• the mass of accumulated wad on the filter of the pneumatic hopper is finally measured.
• the wad yield obtained is expressed in mg / kg.
• This test is identical in its test application described in point 1 but is applied this time after the pneumatic transport test.
• This test consists of simulating a pneumatic transport under high pressure, son cuts or granules. This test is much more severe than the transport that we can find in an industrial environment makes it possible to subject the products to very important solicitations.
• a quantity of 50 grams of product is rotated in a stainless closed circuit for 45 seconds and at a pressure of 5 bar (0.5 MPa).
• This test makes it possible to solicit the product in motion and to evaluate its resistance to friction produced on product, as well as product on stainless steel wall. After the test, the product is recovered and sieved, so as to separate the flock. The result of this test is expressed in Table 3 as a percentage of wad formed as a function of the initial mass of product.
• the glass content obtained on the finally obtained composite part was measured for the long cut yarns and the granules using the device described with reference to FIG. 1, the mixture in the hopper being obtained by weighing by a gravimetric system marketed by Maguire society.
• the fibers or granules are mixed into the hopper in proportions adjusted to obtain on the final composite part a glass content of 30% by weight.
• these, whose glass content of 30% is already predetermined are of course introduced alone in the hopper, ie without mixing with a vector of the glass component.
• FIGS. 2a, 2b, 2c give the glass levels (TV) as a function of the number of the part manufactured during the successive cycles, respectively when a granule according to example 3 (FIG. 2a), a granule according to example 4 ( Figure 2b) or long cut son according to Example 1 ( Figure 2c) are used to supply fiberglass hopper.
• a zero value in FIG. 2c means that the flow of the cut wires could not be made during the corresponding cycle because of the formation of bridges.
• Example 9 The dispersion of the fibers within the composite part finally obtained was measured on the products of Examples 1, 3, 4 and 5.
• This measurement consists of evaluating the surface part of the part for which the fiberglass is insufficiently dispersed.
• the dispersion of the glass granules or glass filaments in the thermoplastic matrix is evaluated after the mixture has been injected onto a plate of thickness equal to 2 mm and the dimensions of which are controlled.
• This measurement consists of evaluating the area occupied by clusters of undispersed fibers within the plate.
• the undispersed filaments can be found both within the plate itself and on the surface, the small thickness of the plate making it possible to visualize transparently the undispersed filaments inside it.
• the fiberglass is injected by the single-screw device with the thermoplastic material into a mold / counter-mold of specific shape, making it possible to obtain a plate of very small thickness and of perfectly determined dimensions, on which measurements can be made to compare the dispersion of the glass fibers on the different products obtained.
• the plate is placed on a lighting system to darken certain areas of the plate for which fiber clusters from a poor dispersion are present.
• This image is then analyzed by the Mesurim® image analysis software.
• the software makes it possible to transcribe an analysis carried out on a number of pixels, into a result in the form of a percentage of surface having a poor dispersion of the fibers, relative to the total surface of the plate.
• Conditions 1 back pressure of 0 bar on the injection screw and use of a standard screw speed, ie of the order of 130 revolutions per minute.
• Conditions 2 backpressure of 120 bar (12 MPa) applied to the injection screw, to limit its recoil during material mixing during the dosing and injection phases and use of a reduced screw speed (80 rpm per minute) at the end of the dosing.
• Table 4 gives the results obtained for these two modes, for the parts obtained from the semi-products used for the introduction of the glass, described in Examples 1, 3, 4 and 5.
• Example 10 In this example, the mechanical performances of the composite parts made from the long fibers obtained according to Example 1 or the granules obtained according to Examples 3 or 4, from the process according to the invention, were evaluated in the conditions to achieve the best results for each of them.
• the bending fracture stress as well as the Charpy and Izod impact strengths were measured in the conditions defined respectively by ISO 178, ISO 179 and ISO 180.
• the mechanical properties of the composite parts obtained from the process according to the invention are comparable to those of composite parts obtained from thermoplastic granules of the prior art.

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• Injection Moulding Of Plastics Or The Like (AREA)

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• 2005
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