Impact-resisting composites

SWEDEN (19) SEE

<img file="SE429987B_D0001.tif" />

PATENT AUTHORITY (12) PUBLISHING LETTERS (Bl KU 7305542-3 (5)) International Class' £ Q4 B 1/98 // E 04 C 2/22,

E 04 C 5/07 (44) AnsOkan outsourced and outsourced ββ-10-10 petition published (41) Application generally available 78-11-18 (22) Patent application filed 78-05-16 (24) Lopdag (62) Stamansokans number (86) International filing date (86) Filing date for European patent application (30) Priority information (II) Publication JQQ QQ7 number beer

The application came as (S Swedish patent application

Q Completed International patent application with number

Q converted European patent application with number

W 601 «8 SCI d'.lv Fine LQ QIC lStlUB bW-C QV

77-05-17 AU 123/77 (71) Applicant: Commonwealth Scientific and Industrial Research Organization Campbell AU (72) Inventor: MD Campbell Ashwood (74) 0mbud: Holmqvist L (54) Title: Composite material (56) Published publications: FR 2 118 861 (E04C 5/00)

NO 98121 (EQ4C 5/08)

CH 562 937 (E04C 5/07)

DE 916 113 (E04C 5/07)

DE 1 509 009 (E04C 5/07)

US 2 425 883 (52-309)

US 3,605,361 (52-223)

7805542-3

The present invention relates to a composite material.

The object of the invention is to provide a reinforced material which can be used as an energy absorbing building element in the preparation of buildings and in the manufacture of objects for which fracture safety and energy absorbing properties are desirable.

In accordance with the invention there is provided a composite material comprising a substantially continuous matrix consisting of curable polymers, thermoplastic polymers, gypsum, cement, mortar, concrete or metals, embedded in a plurality of reinforcing elements of higher tensile strength than the matrix, wherein the reinforcing elements comprise metallic filaments. filaments, polymeric filaments, boron filaments, plant fibers or twisted paper, each reinforcing member being separated from the matrix by a continuous, helical sheath or winding of flexible material bonded to the matrix comprising paper, metal wire, metal foil, polymer film, polymer filament or ceramic fiber, the strength of the winding being such that the winding undergoes a lower tensile load than the reinforcing element and that the construction and arrangement of the winding is such that when the composite material is loaded with a tensile force along the axis of the reinforcing element, the winding is contracted over the reinforcing element and thereby increasing the co-operation the element until the point is reached when the winding breaks and thus the reinforcing element is allowed to slide into winding.

7M5542-3

matrix

The matrix consists of a material which can solidify on the basis of the liquid state. The function of the matrix is ​​to transfer load between the windings in the reinforcing elements. It is important that the matrix does not infiltrate the winding to any great extent since the frictional property of the bond between the reinforcing element and the winding can be lost and thus the toughness of the composite material will be reduced. As the reinforcing elements are loaded during compression along their longitudinal axes, the matrix also serves to inhibit the formation of dents.

Suitable materials for the matrix include curable polymers such as urea-formaldehyde resins, polyesters, epoxy and phenolic resins; thermoplastic polymers such as bitumen, polyethylene, polyvinyl chloride and polypropylene; and inorganic compounds and compositions, such as plaster, cement, mortar and concrete. In some applications, a metal matrix, such as aluminum or copper, can be used.

reinforcing element

The reinforcing element must have a higher tensile strength and preferably have a higher modulus of elasticity than the matrix. In the ideal case, the reinforcing element consists of a monofilament or multiple filaments where the filaments extend in parallel. In the case of an element of multiple filaments, the mechanical properties, especially the compressive strength of the parallel to the filaments, for the composite material can be improved if the filaments are bonded together. The reason for this is that the load transfer between the mutual filaments is improved. If multiple filaments are used, they may be discontinuous provided the discontinuities do not coincide. When discontinuous forms of pelvic filaments are used, additional energy must be absorbed in fracture due to the drawing of these filaments. Multiple filaments can also be wound together to obtain the reinforcing elements.

Suitable reinforcing elements include metal filaments, such as steel, titanium and copper wires; ceramic filaments such as carbon and glass fibers; polymeric filaments such as nylon, aramid and polypropylene fibers; boron fibers; plant fibers, such as sisal and cotton; and twisted paper.

COVER

The housing should preferably be continuous or continuous, flexible and either in the form of a strip or filament. Single or multiple type housings can be used. During manufacture, the casing is wrapped tightly around the reinforcing element in a helical manner. The stress applied during winding and the spiral angle can be optimized for a particular application of the material.

Adjacent coils should preferably have opposite directions to prevent deformation of the composite, and this is especially necessary if winding materials are used which are dimensionally unstable due to

7805542-3 temperature or moisture. When elements comprising a plurality of windings are used, the winding direction can be varied. These elements can further be braided. If the casing or core is made of a material which is highly sensitive to water, for example paper, the composite material and / or the wound element may require a coherent, waterproof coating.

Suitable winding or wrapping materials include paper; metal wire or metal foil such as steel, aluminum and copper; polymeric filaments such as nylon, aramid and polyester; ceramic fibers, such as carbon and glass fibers; and plant fibers, such as sisal, hemp and cotton.

No special orientation of the reinforcing elements in the composite is required. However, optimum gasket and optimum mechanical properties are achieved as the longitudinal axes of the elements extend in the direction of the principal stresses.

Since a material thus oriented, containing continuous reinforcing elements, is loaded by a pulling force parallel to the longitudinal axes of the elements, the load is transferred between the winding of the reinforcing elements by the matrix and between the outer winding of the element and the reinforcing element itself by frictional forces. As the applied load increases, the winding is extended longitudinally and its diameter is reduced and consequently the normal stress between the winding and the reinforcing element increases. This results in an increase in the frictional forces between the reinforcing element and the winding and as a result, the load transferred to the reinforcing element increases. As the winding undergoes breakage, the reinforcing element is separated from the winding but this occurs at a controlled rate depending on the winding's ability to remain in position due to friction. In this way, a composite material is obtained which absorbs large amounts of energy in the event of breakage and as long as the reinforcing elements do not break, a fracture-resistant element is obtained.

When the oriented composite material is loaded by a compressive force parallel to the longitudinal axes of the reinforcing elements, the helical winding carries the load-bearing reinforcing element towards the formation of dents.

The degree of support is determined by the degree of bias in the winding and the helical angle. As the load is applied, the winding length decreases and the diameter increases.

This causes the reinforcing element to buckle in a stable manner and thus a non-catastrophic failure is obtained.

The combination of reinforcing elements and winding can be used to selectively reinforce an element. For example, a substantial degree of reinforcement and strength gain is achieved in a building component subjected to bending by means of reinforcing or reinforcing materials of low strength and toughness, such as polyurethane foam or twisted paper with high strength elements and high modulus of elasticity only on the tensile and pressure surfaces. Alternatively, the composite material can be used as a core for a material exhibiting high strength, high elastic modulus and low toughness, for example with carbon fiber reinforced epoxy resin.

The composite material can be used in any device which requires energy absorbing and fracture resistant properties. Such devices as shock absorbers for cars, motorway handrails, stationary shock absorbers (for example, in car garages) and fenders intended for boats and railway wagons, flywheels, guides and fasteners for seat belts can be made of composite materials, which preferably contain parallel arms. Energy-absorbing sheets can also be made using either random or selectively oriented, for example, woven or knitted reinforcing elements. The composite material is suitable for pressure wave and shock absorbing structures, for example cyclone-proof housing and transport containers. The fracture safety properties of the composite material can be appropriately utilized for ladders, scaffolding, molds and lining for tunnels. The composite material can endure very large deflections before reaching the maximum load point.

The composite material can be prepared using such procedures as pultrusion, injection molding and coextrusion. If a foamed plastic pulp is used, the composite material can be prepared by in situ foaming.

The amount of energy absorbed by the composite material during fracture has been found to be substantially independent of the extent to which the load is applied. The composite material can be described as substantially insensitive to notch formation. This is due to the inability of the reinforcing elements to form spreads.

Preferred embodiments of the invention will now be described with reference to the accompanying drawings, in which Fig. 1 is a perspective view of a composite material according to the invention that has undergone a load applied perpendicular to the reinforcing elements; Fig. 2 is a perspective end view of further Fig. 3 is a perspective view of a reinforcing element with a casing or winding for use in composite material; 4 is a perspective end view of a further embodiment of the composite material according to the invention, and Fig. 5 is a plan view of a woven composite material.

Referring to Fig. 1, a composite material comprising a polyester matrix 1 is embedded in which is embedded nine sisal reinforcement elements 2.

Each reinforcing element is wrapped or wrapped with paper 3. The composite material has been molded to form an extended building element with a square section, the reinforcing elements 2 extending in the longitudinal direction of the element. For illustrative purposes, the element has been subjected to breakage by a force acting in the direction XX. It will be appreciated that although the matrix and the casing have undergone breakage, the building element is still held together by sisal reinforcing elements 2.

Figure 2 shows an energy-absorbing lightweight composite material.

7805542-3

This material comprises a plurality of reinforcing elements comprising twisted paper strands 4 extending along a circular section element at its periphery. The casing 5 is a paper casing and the matrix 6 is a foamed polyurethane.

Fig. 3 illustrates a preferred method of winding a reinforcing element. In this case, a sisal reinforcing element 7 is spirally wound with four paper strips 8a, 8b, 8c and 8d.

In Fig. 4, a composite material is shown comprising a matrix 9 of epoxy resin, in which is embedded reinforcing element 10 of glass fibers with wrapped paper 11. The matrix of epoxy resin is further reinforced with carbon fibers 12 outside the core of the elements.

Fig. 5 illustrates a composite material comprising a woven paper of glass-coated glass 13 embedded in a polyester matrix 14.

EXAMPLE 1

Reinforcing elements of a sisal rope having a diameter of about 2.5 mm, where the filaments are substantially parallel, were wound with four overlapping layers of sack kraft paper (44 grams), 30 mm wide. The resulting wound element had an outer diameter of about 5 mm. Ten of these wound elements are coated with Monsanto Polyester resin D3679 polyester resin containing a tert.butyl benzoate catalyst in 0.6% amount, arranged in two layers in a 25 mm wide mold and pressed at a temperature of 130 ° C and at a pressure of 2.8 MPa for 15 minutes. The element thus obtained was tested for flexural strength. A similar composite material was prepared from 16 coiled four-layer elements in a 19 mm mold and tested for impact strength. The specific gravity of the composite materials was 1.1 and 20% by weight of resin matrix was used.

The fracture modulus for this material was 87 MPa and the impact toughness of an isod test for a 19 mm square uncut specimen was 31 J. This value was an underestimate as the specimen was not broken into two parts.

EXAMPLE 2

In this example, a composite material similar to that described in Example 1 was prepared except that the specimens had an inner section, where the reinforcing elements consisted simply of spirally wound 30 mm strip of sack kraft paper (3 mm in diameter). Bending strength test specimens were prepared as in Example 1 with two layers of six twisted paper strips arranged between the layers of wound reinforcing elements. The impact test specimens included an outer single layer of four to five wound sisal elements and an inner section of eight twisted paper elements. The specific weight of the composite materials was 1.1 and 20% by weight of resin was used.

The fracture modulus for this composite was 113 MPa and the impact toughness of the izod sample for a 19 mm square non-scored specimen exceeded 40 J.

7805542-3

The test piece did not undergo a crime in a clean way.

EXAMPLE 3

For comparative purposes, a composite material was prepared in the same manner as in Example 1 using the spiral twisted paper strips described in Example 2 as reinforcing elements as follows:

For flexural strength testing, two layers of seven;

For impact testing, six layers of five.

The composite material had a specific weight of 1.1 and 32% resin was used.

The fracture modulus for this material was 90 MPa, and the impact toughness of the isod specimen for a 19 mm square non-scored specimen was 10 J. The specimen underwent fracture with a clean fracture surface and did not exhibit the toughness or fracture safety properties characteristic of the composite materials of the invention.

MECHANICAL PROPERTIES OF THE COMPOSITE MATERIAL

While it is difficult to make a proper comparison of mechanical properties between different materials, some indication of the relative behavior of a composite material in which the wound element construction is utilized can be obtained by a comparison with two timber types of building quality, namely Eucalyptus rain (hard wood) ) and Pinus radiata (soft wood) with 12% moisture content.

TABLE 1

<td>Physical property</td><td>Eucalyptus regnans</td><td>Pi nus radiata</td><td>Composite Material (Example 2)</td>

<td>3 Density (g / cm)</td><td> 0,7</td><td> 0,5</td><td> 1,1</td>

<td>Crash Module (MPa)</td><td> 137</td><td> 80</td><td> 113</td>

<td>Bending Proportion Limit (MPa)</td><td> 90</td><td> 46</td><td> 75</td>

<td>Elasticity Module (GPa)</td><td> 16,9</td><td> 10,2</td><td> 8,5</td>

<td>Impact toughness in Iodine test (J)</td><td> 22</td><td> 88</td><td>&gt; 40 (/ -βθ)</td>

It is evident from Table 1 that the impact toughness of the composite material is significantly greater than the impact toughness of each of the timers. The bending properties are an indication of what can be achieved by using a reinforcing element wrapped with sisal. If a core material with a higher bending modulus was used, the bending strength properties would be better.

EXAMPLE 4

Three composite materials were prepared by die casting using a Monsanto M750 polyester containing as catalyst T% benzoyl peroxide at a temperature of 150 ° C for 10 minutes. The specimens were 400 mm long and had a cross section of 15 x 15 mm. The test pieces of the composite materials

7805542-3 was scored and the energy at the fracture surface was measured by the method described by MJ CHAPPELL and JG MORLEY in The fracture toughness of conventional materials and composite systems containing non fracturing reinforcing elements: Journal of Materials Science, Vol. II, (1976), p. 57-70, (ref. 1).

Composite material 1

The reinforcing elements consisted of E-type multiple glass filaments with a total weight of 28 g / m. The winding or cover consisted of electrical grade paper having a width of 6 mm and a weight of 0.20 g / m. The total wound element had a diameter of 0.8 mm. 8% by weight polymer matrix was used. 480 reinforcing elements were used.

Composite material 2

The reinforcing elements consisted of E-type multiple glass filaments with a total weight of 28 g / m. The winding consisted of kraft paper with a width of 12 mm and a weight of 0.51 g / m. The entire diameter of the wound element was 1.0 mm. 30% by weight polymer matrix was used. 260 reinforcing elements were used.

Composite material 3

The reinforcing elements were made of continuous multiple nylon filament tire type filaments with a total weight of 0.11 g / m 2. The winding consisted of two layers of kraft paper each with a width of 12 mm and a weight of 1.1 g / m. The entire diameter of the wound element was 1.3 mm, 9 weight X polymer matrix was used, as were 135 reinforcing elements.

The results of the fracture surface energy tests are shown in Table 2 together with results for other materials found in the above-described reference 1. The superior energy absorbing ability of the composite materials is evident. However, these composite materials do not represent the limit of the energy absorbing ability of these materials.

TABLE 2

COMPARATIVE BREAKFAST ENERGY

MATERIAL AVERAGE SHIPPING SPECIFIC WEIGHT SPECIFIC SHIPPING ENERGY ENERGY (Jm “² x 10 "⁴) (Jm^d x 10 '^

<td colspan="4">Composite</td>

<td>material 1</td><td> 8,4</td><td> 1,4</td><td> 6,1</td>

<td>Composite material 2</td><td> 5,9</td><td> 1,3</td><td> 4,4</td>

<td>Aluminum</td><td> 8,6</td><td> 2,7</td><td> 2,9</td>

<td>Composite material 3</td><td> 2,6</td><td> 0,96</td><td> 2,7</td>

<td>Soft carbon steel</td><td> 4,8</td><td> 7,8</td><td> 0,6</td>

<td>All aluminum alloy</td><td> 2,1</td><td> 2,8</td><td> 0,8</td>

<td>tEAK-TREE</td><td> 0,8-1,6</td><td> 0,8</td><td> 1,0-2,0</td>

<td>Epoxy resin</td><td> 0,1</td><td> 1,2</td><td> 0,1</td>

<td colspan="2">Polymethyl methacrylate 0.1</td><td> 1,2</td><td> 0,1</td>

7805542-3

EXAMPLE 5

A set of oriented composite materials listed in Table 3 was prepared by die casting. The materials were subjected to a three-point bending test with a span to depth ratio of 16: 1. The various properties of the composite materials obtainable are shown in the table.

7605542-3 iZ

Di&gt; Ll t — i (OO CL lu x CL tn

IN

P * tn &lt;&lt;- * Lu for _) Q.

-JS pC '-w * X

X ΗΧΟ LU CO X

Q

O s— · X for X D_ £&gt; s co * lo oo oo mom

OJ r00 C0 oo ​​lo στ oj

LO OJ

CO 'F- LO «0 *

LO F- r- rCO OJ «- ΓΟΟ

CO

F στ f lo LO «0o tn

OH

COMPOSITIVE MATERIAL PROPERTIES * zi — i

Lu

U-4

Ο Κω lz cl ►— »GQ&gt;

&lt;

&lt;/&gt;

CO &lt;fes X l Q tn Z FX iZ oi 1— &lt;CD&gt;

IN

Q &lt;X CO X tn OZ &lt;CD S

CZ lil

F * _l LU h- &lt;2 O&gt; -h S Η- Ω &lt;

CO &lt;

CO

IN

CO

CD

Tue LU LU XX LU oi _J &lt;C LU &lt;·

<td>O</td><td>O</td><td>O</td><td>O</td><td>O</td><td>O</td><td>O</td><td>O</td><td>O</td><td>X</td>

<td>O</td><td>O</td><td>m</td><td>O</td><td>LO</td><td>O</td><td>O</td><td>O</td><td>O</td><td>X</td>

<td>LO</td><td> «0*</td><td>στ</td><td>F</td><td> «0*</td><td>OH</td><td>O</td><td>π-</td><td>LO</td><td></td>

<td>r OH</td><td>OH OH</td><td>LD</td><td> 00</td><td>CO</td><td>OH OH</td><td>F</td><td>ΙΩ</td><td>F</td><td>CO F O -P (0 ω</td>

<td>*island*</td><td>Γ--</td><td>OH</td><td>O</td><td>CO</td><td>tn</td><td>· r</td><td>O</td><td>LO</td><td> &gt;&gt;</td>

<td></td><td></td><td></td><td>A</td><td>A</td><td> ·«</td><td></td><td>• t</td><td>A</td><td>p</td>

<td></td><td>OH</td><td>OH</td><td>r</td><td></td><td>P "</td><td></td><td></td><td>OH</td><td>Π3 • P</td>

fo

-X

<td colspan="6"></td><td colspan="4">F Φ CL CL FO</td><td>C φ C ε : fo</td>

<td>CO</td><td>r</td><td></td><td>r</td><td>στ</td><td> 00</td><td>OH</td><td>CO</td><td></td><td>CL</td><td>-Ρ</td>

<td rowspan="2">0J</td><td></td><td></td><td>OH</td><td>r</td><td></td><td>OH</td><td>p</td><td>Π-</td><td></td><td>ω</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> +-&gt;</td><td>FO</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>(ISLAND</td><td>&lt;Ρ</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>C</td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>C</td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>•in-</td><td></td>

<td> &gt;&lt;</td><td></td><td></td><td>X</td><td></td><td>X</td><td>X</td><td></td><td>X</td><td> &gt;</td><td>ω</td>

<td>cz</td><td></td><td></td><td>oz</td><td></td><td>oz</td><td>OZ</td><td></td><td>oz</td><td>• P</td><td>Ρ</td>

<td>lxj</td><td></td><td></td><td>LU</td><td></td><td>LU</td><td>LU</td><td></td><td>LU</td><td></td><td></td>

<td> 1—</td><td></td><td></td><td>F ·</td><td></td><td> 1—</td><td>F *</td><td></td><td> 1—</td><td> &gt;</td><td>• ι-</td>

<td>CO</td><td></td><td></td><td>tn</td><td></td><td>tn</td><td>tn</td><td></td><td>tn</td><td>(ISLAND</td><td> &gt;</td>

<td>LU</td><td> +</td><td> +</td><td>LU</td><td> +</td><td>LU</td><td>LU</td><td> +</td><td>LU</td><td rowspan="2">FO</td><td></td>

<td> &gt;-</td><td></td><td></td><td> &gt;-</td><td> •</td><td> &gt;-</td><td> &gt;-</td><td> •</td><td> &gt;-</td><td>m</td>

<td> _]</td><td>Lu</td><td>Lu</td><td>_IN</td><td>Lu</td><td></td><td> _1</td><td>Lu</td><td> —-1</td><td>c</td><td>LO</td>

<td>O</td><td></td><td></td><td>O</td><td> •</td><td>O</td><td>O</td><td> •</td><td>O</td><td>F</td><td></td>

<td>CL</td><td>X</td><td>X</td><td>CU</td><td>X</td><td>CL</td><td>D_</td><td>X</td><td>CL</td><td>IFO</td><td> •</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>t-4</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>_Λ</td><td>F)</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>-Ρ</td><td> •</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>_x</td><td> 1—4</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>• r * ·</td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>C i—</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ω</td><td>• Fo</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>F</td><td>F r—</td>

<td> 00</td><td></td><td>LO</td><td>CO</td><td></td><td></td><td></td><td></td><td></td><td>Φ</td><td>ψ. φ</td>

<td>A</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>-Ρ</td><td>CL</td>

<td>O</td><td>•island^-</td><td>CO</td><td>t.</td><td>lf&gt;</td><td>OH</td><td>LO</td><td>στ</td><td>r— ·</td><td>-Ρ</td><td>ω £</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>4-s φ FX</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>• fo</td><td>FOR LU</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Q.</td><td>JZ X · Γ-</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>«Ρ</td><td>&gt; T _</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ω</td><td>_c ε</td>

<td>1 CZ</td><td>1 CZ</td><td>t cz</td><td>1 OZ</td><td>1 CZ</td><td>1 oz</td><td>1 CZ</td><td>t oz</td><td>1 cz</td><td>FO</td><td>Φ o</td>

<td>F · LU</td><td>1— LU</td><td>1— LU</td><td>1- LU</td><td>F · LU</td><td rowspan="2">toi</td><td>F- LU</td><td>F- LU</td><td>I— LU</td><td>X</td><td>X (Λ</td>

<td>Lu q.</td><td>Lu Cl</td><td>LU Q-</td><td>LU D.</td><td>Lu D.</td><td>Lu CL</td><td>Lu CL</td><td>LU CU</td><td>C</td><td>n</td>

<td>δδ</td><td>&lt;CL Di &lt;</td><td>δδ</td><td>&lt;D. OZ &lt;</td><td>δδ</td><td>&lt;Dl. Di &lt;</td><td>δδ</td><td>&lt;CL cz &lt;</td><td>&lt;DOZ &lt;</td><td>φ</td><td>for</td>

<td rowspan="2">: z cl</td><td>CL</td><td>^ z cu</td><td>SZ CL</td><td>iZ CL</td><td>iZ CL</td><td>iZ CL</td><td>LZ CL</td><td>iZ D.</td><td>• Ρ</td><td>FB</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>C</td><td>O Fri</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>φ</td><td>q- (/)</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>CZ</td><td></td><td>ε</td><td> 1</td>

<td></td><td></td><td>_u</td><td></td><td></td><td></td><td></td><td>LU</td><td></td><td>φ</td><td>fÖ u</td>

<td>L-</td><td></td><td> &lt;</td><td></td><td></td><td></td><td></td><td>CL</td><td></td><td>Γ-</td><td></td>

<td>X</td><td></td><td>P</td><td></td><td></td><td></td><td> 1</td><td>CL</td><td></td><td>Φ</td><td>FF</td>

<td>LU</td><td> &lt;</td><td>tn</td><td> |</td><td></td><td>IN</td><td>Z</td><td> &lt;</td><td>O</td><td></td><td>X φ</td>

<td>X</td><td>F *</td><td></td><td>"C</td><td></td><td>X</td><td>LU</td><td>CL</td><td> °&lt;</td><td>Φ</td><td>-P</td>

<td> &lt;</td><td rowspan="2">tn</td><td>O</td><td></td><td></td><td>X</td><td>CL Ι-</td><td></td><td>OZ</td><td>χ</td><td>ii ω</td>

<td></td><td rowspan="2">iZ</td><td>U * 4</td><td></td><td> 4—4</td><td>Ο X</td><td> 1—</td><td>hrs-</td><td>FO</td><td>φ</td>

<td> &gt;—4</td><td>F ·</td><td>Lu</td><td></td><td>X</td><td>CZ LU</td><td> &lt;</td><td>oz</td><td>X</td><td> • *</td>

<td>Lu</td><td>LU</td><td>f</td><td>X</td><td></td><td> 1-4</td><td>CL X</td><td>X</td><td>eC</td><td>c</td><td>Lu i—</td>

<td>CO</td><td>CD</td><td>Li</td><td>O F-</td><td> &lt;</td><td>X Ω</td><td> &gt;- &lt;</td><td>X</td><td>CL</td><td>'Γ^-</td><td>• Oh</td>

<td> &lt;</td><td>δ</td><td>X X</td><td>-JX&gt; - LU</td><td>tn 1 in</td><td>3δ</td><td>xj —J O HH</td><td> 1—4 5*</td><td>CL O</td><td>-r</td><td>X CL</td>

<td>CD</td><td>Q</td><td>X</td><td>XX</td><td>tn</td><td>&lt;H</td><td>CL Lu</td><td>hrs</td><td>iZ</td><td>X</td><td>+ X</td>

7805542-3. EXAMPLE 6

Two sheets of composite material were prepared by die casting using a Monsanto M750 polyester with 1% benzoyl peroxide catalyst and a curing temperature of 150 ° C per 10 minutes.

Composite material 1

The wound reinforcing elements were of the type described under composite material 3 of Example 4. These elements were woven into a mat of four elements per cm in the warp and weft.

Composite material 2

The wound reinforcing elements were of the type described under composite material 2 of Example 4. Two layers of these elements were cross-laminated.

In a screening test using a GE Boxboard type test apparatus in accordance with the TAPPI specification, the composite materials were found to have penetration resistance similar to the equivalent size for 0.5 mm soft carbon steel sheet.

In particular, it should be noted that the term matrix "as used in the specification and claims relates to any material which can be solidified from the liquid state and remain solidified after the composite is formed, but that rubber-like, elastomeric materials are excluded.