US20190263085A1

US20190263085A1 - Thermoplastic Bonded Preforms and Thermoset Matrices Formed Therewith

Info

Publication number: US20190263085A1
Application number: US16/289,057
Authority: US
Inventors: Mark Janney; Mark Mauhar
Original assignee: Carbon Conversions Inc
Current assignee: Carbon Conversions Inc
Priority date: 2016-02-19
Filing date: 2019-02-28
Publication date: 2019-08-29
Also published as: EP3416795A1; US10406776B2; MX2018009926A; CA3014638C; US20170239909A1; WO2017142868A8; WO2017142868A1; EP3416795A4; CA3014638A1; JP2019508292A

Abstract

A thermoplastic bonded preform and method of manufacturing the preform are disclosed. The preform comprises a primary fiber comprising little or no sizing; a mechanical fiber; and a thermoplastic.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the priority benefit under 35 U.S.C. section 119 of pending U.S. Provisional Patent Application No. 62/297,368 filed Feb. 19, 2016 and U.S. Provisional Patent Application No. 62/297,455 filed Feb. 19, 2016 both of which are incorporated by reference.

FIELD OF THE INVENTION

The present invention is related to thermoplastic bonded preforms, their formation and the use of thermoplastic bonded preforms as a reinforcement in thermoset matrices.

BACKGROUND

Fiber reinforced plastics have found wide spread use in many applications due to their excellent strength to weight ratio as compared to metals and other materials. The demand for some materials, such as carbon reinforced plastics, has increased to the point where fiber supply is challenged and cost has risen accordingly. This has lead to a desire to reuse fibers, particularly carbon fibers, in an effort to augment supply, decrease cost, and convert a material, which is otherwise scrap, into a repurposed component of a product.
The surface of carbon fiber is difficult to work with as there is little that will bond thereto. Carbon fiber is therefore typically treated, in a process referred to in the art as “sizing”, whereby the surface of the carbon fiber is chemically modified to improve the bonding characteristics of the fiber allowing the fiber to be incorporated into a matrix as a reinforcement.
During most carbon fiber recycle operations the sizing is unfortunately removed, or compromised, thereby rendering the carbon fiber very difficult to work with. Carbon fibers with little or no sizing have a low bulk density and the fibers tend to become airborne easily due to the lack of adhesion between fibers. Virgin fiber, which has not been sized, has the same problems and there is a parallel need to utilize virgin fiber along with, or instead of, recycled carbon fiber. Resizing the recycled carbon fibers is not cost effective and not a viable operation commercially.
There is a significant desire in the art for methods to utilize a recycled fiber, particularly with little or no sizing, in a form which is compatible with subsequent operations. The present invention provides fibers, and particularly carbon fibers with little or no sizing, as a thermoplastic bonded preform suitable for use in subsequent applications particularly as a reinforcement in a thermoset matrix composite.

SUMMARY OF THE INVENTION

The invention relates to a method of incorporating fibers, and particularly carbon fibers with little or no sizing, into a composite as a thermoplastic bonded preform.
A particular feature of the invention is the ability to utilize recycled, or virgin, carbon fiber without the requirement of resizing or otherwise chemically modifying the fibers.
An advantage of the invention is the ability to incorporate carbon fiber as a thermoplastic bonded preform for subsequent use.
These and other embodiments, as will be realized, are provided in a thermoplastic bonded preform comprising a primary fiber comprising little or no sizing; a mechanical fiber; and a thermoplastic.
Yet another embodiment is provided in a method of forming a thermoplastic bonded preform. The method comprises:
forming a blend comprising solvent, a primary fiber comprising little or no sizing, a mechanical fiber and a thermoplastic;
forming an unconsolidated preform of the blend wherein the unconsolidated preform comprises the primary fiber, the mechanical fiber and the thermoplastic; and consolidating the unconsolidated preform under heat and pressure to form the thermoplastic bonded preform.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a graphical illustration of an embodiment of the invention.

DESCRIPTION

The present invention is related to an improved method for incorporation of fibers, particularly fibers with little or no sizing, to form a thermoplastic bonded preform. More specifically, the present invention is related to the formation of a thermoplastic bonded preform and a thermoset matrix comprising the thermoplastic bonded preform as a reinforcement referred to herein as a thermoplastic bonded preform reinforced thermoset.
A thermoplastic bonded preform is a nonwoven composite comprising a primary fiber, a mechanical fiber and a thermoplastic fiber. As will be realized from further discussion, a primary fiber, mechanical fiber and thermoplastic are formed into a composite which is a thermoplastic bonded preform for subsequent use as will be described more specifically herein.
The primary fibers are preferably carbon fiber and most preferably a discontinuous or chopped carbon fiber. Carbon fiber with little or no sizing is suitable for demonstration of the invention and the ability to use fibers with little or no sizing demonstrates a particular advantage offered by the invention. The term “little or no sizing” refers to a carbon fiber which has either been recycled, and therefore the sizing has been eliminated, compromised, or significantly reduced to between 0.0 and 0.5% of the carbon fiber weight, or the carbon fiber is a “virgin fiber” which is a term of art indicating the fiber is in the “as manufactured” condition. Fiber with sizing can be used in the process, however, the advantages offered by the invention are more appropriately realized with fibers having little or no sizing. The carbon fiber length and thickness is not particularly limiting herein. Fibers with a length of about 0.254 cm to 5 cm (0.1 to 2 inch), and more preferably 0.508 cm to 1.78 cm (0.2 to 0.7 inches) are suitable for demonstration of the invention. Readily available carbon fibers typical have diameters between about 5 and about 9 μm. The size and high stiffness of the fibers, typically at least about 30 Mpsi, typically forms a very low density nonwoven when air laid. The fibers typically pack in a random nature due to the lack of any inter-fiber adhesion.
The mechanical fibers are preferably highly fibrillated fibers which physically adhere the carbon fibers in a mat especially after densification. The choice of mechanical fiber is not particularly limited with the proviso that they can adhere to carbon fibers, particularly with little or no sizing, and can be adequately wet by molten or viscous thermoplastic. Particularly preferred mechanical fibers include cotton linter, fibrillated cellulosic fiber, fibrillated acrylic fiber and fibrillated aramid fiber.
The thermoplastic is not necessarily limited herein. The thermoplastic can be used as a fiber, or any form which allows intimate mixing prior to forming such as a powder of flake. Fibers are preferred for manufacturing simplicity. Any thermoplastic is appropriate for this application. Examples include, but are not limited to, polyethylene (PE), polypropylene (PP), polyesters such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyamides (PA) such as nylon 6 (PA6) or nylon 66 (PA66), polycarbonate (PC), polyphenylene sulfide (PPS), polysulfones such as polyethersulfone (PESU) or polyphenylsulfone (PPSU), polyetherimide (PEI), polyether-ether-ketone (PEEK), polyether-ketone-ketone (PEKK), and blends of the above fibers.
In a preferred process of forming the thermoplastic bonded fiber a discontinuous primary fiber, a mechanical fiber and a thermoplastic is dispersed in a solvent, with water being preferred, to form a blend. The blend preferably comprises a solids content of 15-94.5 wt % primary fiber, 0.5 to 5 wt % mechanical fiber and 5 to 84.5 wt % thermoplastic. More preferably the blend comprises a solids content of 70-94 wt % primary fiber, 1 to 5 wt % mechanical fiber and 5 to 30 wt % thermoplastic.
The blend is formed as a web The web may be formed on a wet lay forming machine such as a RotoFormer, an inclined wire or a Fourdrinier. Alternatively, the web can be formed by a dry lay or air lay process such as carding or needle punching. The wet laid web is dried after formation to form an unconsolidated preform.
The unconsolidated preform is densified under heat and pressure, as will be more fully described herein, to increase the density thereby forming a densified thermoplastic bonded preform with a higher density than the unconsolidated preform.
The bulk density of the unconsolidated preform is typically less than about 0.2 g/cm³and can be as low as 0.05 g/cm³. The consolidating pressure should be sufficient to increase the bulk density above that of the unconsolidated preform. It is preferable for the densified thermoplastic bonded preform to have a bulk density of at least 0.25 g/cm³up to about 1.0 g/cm³. A density below about 0.25 g/cm³is insufficient to realize the advantages of the invention in most subsequent uses and a density above 1.0 g/cm³is difficult to achieve with reasonable pressures, temperatures and times. The fiber volume fraction that can be achieved in the thermoplastic bonded preform is generally dictated by the amount of pressure that is applied during consolidation. The higher the consolidating pressure, the higher the density of the composite.
Consolidation pressures from about 30 kpa to about 14,000 kpa are suitable for demonstration of the invention. Pressure can be applied using a vacuum bag, a compression molding press, a laminating press, a series of calenders, a double belt press, or other suitable consolidation operations. The thickness of a 17 wt % PP bonded recycled carbon fiber as a function of applied pressure is illustrated in FIG. 1 wherein the thickness is indicated to decrease as the log of applied pressure increases. It is preferable that the consolidation pressure remain until the composite cools at last to below its glass transition temperature or its melting point and more preferably to a temperature of no more than 60° C. and most preferably to ambient temperature of about 25° C.
The consolidating temperature should be above the glass transition temperature (T_g) of an amorphous thermoplastic, such as PC or PEI, or above the melting point (T_m) of crystalline or partially crystalline polymers, such as PA, PET or PPS, to ensure good bonding between the thermoplastic and both the primary fiber and mechanical fiber. The temperature is preferably high enough that the polymer flows well and bonds to the carbon fibers. The appropriate consolidation temperature is a function of the polymer being used and is best determined through a series of experiments.
The thermoplastic bonded preform may be in a fibrous form, sheet form or molded form and can be either flat, as in a platelet shape, or they may have any three dimensional shape, as in a 3-DEP® preform.
The consolidated preforms have sufficient mechanical properties to be cut into smaller, dimensionally stable pieces, which may be further processed.
In a particularly preferred embodiment the thermoplastic bonded preform can be infiltrated with thermoset resin thereby forming a composite which is a thermoplastic bonded preform reinforced thermoset.
To demonstrate a thermoplastic bonded preformed reinforced thermoset composite the thermoplastic bonded preform is preferably infiltrated with thermoset resin. The method of infiltration is not particularly limited herein and can be achieved using liquid compression molding, vacuum infusion, resin transfer molding, etc.
Thermoset resins are selected from acrylic resins, polyesters, vinyl esters, epoxies, polyurethanes and furan.

EXAMPLES

A series of aqueous slurries were prepared comprising solids in the ratios set forth in Table 1 wherein “BAL RCF” refers to the balance of the solids content being recycled carbon fiber. Preforms were formed using a conventional wet laid, nonwoven process. The preforms comprised 1.27 cm (0.5 inch) long recycled carbon fiber (RCF), with little or no sizing, with fibrillated para-aramid fiber as a mechanical binder fiber and a thermoplastic fiber as listed in Table 1. The wet laid thickness (after drying), molded thickness, ratio of wet laid thickness (T_w) to molded thickness (T_m), bulk density, molded density vol %, percentage of molded density attributable to recycled carbon fiber (RCF FVF), molded air permeability and molding temperature are provided in Table 1. Permeability of the preforms are given in Tables 1, 2, and 3. As shown in Tables, 1, 2, and 3, the addition of a thermoplastic binder to the preform composition followed by the application of pressure at elevated temperature resulted in a greatly increased density of the thermoplastic bonded preform after cooling. The as-fabricated, wet-laid preforms had bulk densities between 0.06 and 0.13 g/cm³. The densified thermoplastic bonded preforms achieved densities between 0.46 and 0.80 g/cm³.
All of the consolidated preforms had enough strength to be cut into smaller, dimensionally stable preforms for subsequent processing.

TABLE 1

Thermoplastic-bonded carbon fiber preforms-thickness density, FVF, and permeability.

Preform

Thickness

Bulk Density

Molded

Molded Air

Molding

Composition	Wetlaid	Molded		Wetlaid	Molded	Density	RCF FVF	Permeability	Temperature
(wt %)	(mm)	(mm)	T_W/T_M	(g/cm²)	(g/cm²)	(vol %)	(vol %)	(cm²)	(° C.)

20% PA6, 3%	6.3	1.00	6.30	0.13	0.800	50.1	34.2	1.40E−08	270
Aramid, BAL RCF
9% PA6, 3% Aramid,	8.5	2.01	4.23	0.09	0.396	23.5	19.4	4.43E−08	270
BAL RCF
9% PA6, 3% Aramid,	8.5	1.47	5.78	0.09	0.541	32.1	26.6	2.54E−08	270
BAL RCF
9% PA6, 3% Aramid,	8.5	1.09	7.80	0.09	0.730	43.3	35.8	1.43E−08	270
BAL RCF
9% PC, 3% Aramid,	12.46	1.25	9.97	0.06	0.621	37.4	31.3	1.68E−08	280
BAL RCF
9% CoPET/PET, 3%	8.25	1.75	4.71	0.10	0.460	26.4	22.3	2.83E−08	141
Aramid, BAL RCF
9% CoPET/PET, 3%	8.25	1.27	6.50	0.10	0.644	36.4	30.8	1.70E−08	270
Aramid, BAL RCF

All samples were made as 800 gsm wet-laid preforms, then compression molded to final thickness.
Air permeability was measured through the thickness of the preforms.

TABLE 2

Density, Thickness, and Specific Volume vs Consolidation Pressure for
17PP/3Aramid/80RCF preforms

Pressure		Compaction				Molded
in 12 × 12		Ratio-	Relative	RCF	Molded	Specific	Air
inch tool	Thickness	Unpressed to	Density	FVF	Density	Volume	Permeability
(psi)	(mm)	Pressed	(vol %)	(vol %)	(g/cm³)	(cm³/g)	(cm²)

11	2.95	3.86	17.6	12.00	0.27	3.69	3.33E−08
28	2.52	4.52	20.6	14.10	0.32	3.15	—
139	1.83	6.23	28.6	19.40	0.44	2.27	2.54E−08
1042	1.02	11.18	50.9	34.80	0.78	1.28	1.37E−08

Test preforms were made at 800 gsm areal density. As-fabricted preform thickness ~11.4 mm

TABLE 3

17PP/3Aramid/80RCF preforms consolidated to 1.0 mm and cooled under
pressure experienced springback after pressure was removed.

	Thickness	Compaction				Molded
PP	after	Ratio-	Relative	RCF	Molded	Specific	Air
Content	Molding	Unpressed	Density	FVF	Density	Volume	Permeability
(wt %)	(mm)	to Pressed	(vol %)	(vol %)	(g/cm³)	(cm³/g)	(cm²)

5	2.10	5.43	22.4	19.40	0.38	2.63	2.82E−08
8	1.44	7.92	33.5	27.40	0.56	1.80	1.87E−08
17	1.02	11.18	50.9	34.80	0.78	1.28	1.37E−08

180 C. pressing temperature

Three compositions of thermoplastic bonded preforms were selected to be made into thermoset composites. After consolidation, the preforms were cut into 6 inch×12 inch (150 mm×300 mm) coupons. Epoxy resin (Prime 20VL, Gurit Services AG, Zurich) was infiltrated into the preforms, cured at ambient temperature, then post cured at 65° C. After curing, the samples were tested in flexure to determine their mechanical properties, Table 4. The strengths and moduli of these samples were similar to those for products made with conventional preforms.

TABLE 4

Properties of PP-bonded carbon fiber preforms and of epoxy-
infiltrated composites made from the same

			Relative		FVF in
		Preform	Density	Porosity	Preform	Composite	Composite
PP	Consolidating	Consolidated	of	of	and	Flexure	Flexure
content	Pressure	Thickness	Preform	Preform	Composite	Strength	Modulus
(wt %)	(kPa)	(mm)	(vol %)	(vol %)	(vol %)	(MPa)	(GPa)

5	7171	2.1	22.4	77.6	19.4	155.3	8.4
8	7171	1.44	33.5	66.5	27.4	207.9	12.5
17	958	1.83	28.6	71.4	19.4	174.9	10.5

Throughout the description the terms “fiber” and “fibers” both refer to multiple fibers equally unless stated otherwise.
The invention has been described with reference to the preferred embodiments without limit thereto. Additional embodiments and improvements may be realized which are not specifically set forth herein but which are within the scope of the invention as more specifically set forth in the claims appended hereto.

Claims

1. A thermoplastic bonded preform comprising:

a primary fiber comprising little or no sizing;

a mechanical fiber; and

a thermoplastic.

2. The thermoplastic bonded preform of claim 1 wherein said thermoplastic bonded preform has a density of 0.25 to 1 g/cm³.

3. The thermoplastic bonded preform of claim 1 wherein said primary fiber is a carbon fiber.

4. The thermoplastic bonded preform of claim 3 wherein said carbon fiber is selected from a recycled carbon fiber and a virgin carbon fiber.

5. The thermoplastic bonded preform of claim 1 wherein said primary fiber has a length of <5 cm.

6. The thermoplastic bonded preform of claim 5 wherein said primary fiber has a length of 0.508 cm to 1.78 cm.

7. The thermoplastic bonded preform of claim 1 wherein said primary fiber has a diameter of between 5 and about 9 μm.

8. The thermoplastic bonded preform of claim 1 wherein said primary fiber has a stiffness of at least 30 Mpsi.

9. The thermoplastic bonded preform of claim 1 wherein said mechanical fiber is a fibrillated fiber.

10. The thermoplastic bonded preform of claim 1 wherein said mechanical fiber is selected from the group consisting of cotton linter, cellulosic fiber, acrylic fiber and aramid fiber.

11. The thermoplastic bonded preform of claim 1 wherein said thermoplastic is selected from the group consisting of polyethylene, polypropylene, polyester, polyamide, polycarbonate, polyphenylene sulfide, polysulfone, polyetherimide, polyether ether ketone, poly ether ketone ketone, and blends thereof.

12. The thermoplastic bonded preform of claim 11 wherein said thermoplastic is selected from the group consisting of polypropylene, polyethylene terephthalate, polybutylene terephthalate, nylon 6, nylon 66, polycarbonate, polyphenylene sulfide, polyethersulfone and polyphenylsulfone.

13. A composite comprising said thermoplastic bonded preform of claim 1 infused with a resin.

14. The composite of claim 13 wherein said resin is a thermoset resin.

15. The composite of claim 14 wherein said resin is selected from the group consisting of epoxy, acrylic resin, polyester, vinyl ester, epoxy, polyurethane, furan, and bis-maleimides.

16-35. (canceled)