TWI247775B - Composite material with high toughness and its manufacturing method - Google Patents

Abstract

Provided is one kind of composite material with high toughness which is formed by superposing several prepregs. These prepregs comprise reinforcing fibers and pure thermosetting resin materials which respectively combine with one face of the strengthening fibers (with heat resistance at 160 DEG C or above) and mixed thermosetting resin material wherein polymer powders are mixed into the mixed thermosetting resin material and the heat-resistant composite material with high toughness which is suitable for mass production, having interleaves to increase toughness, and having an effect of thermosetting resin material modified with polymer powders can thus be fabricated.

Description

1247775 IX. Description of the invention: [Technical field to which the invention pertains] A high-vehicle edge composite material and a method thereof. Knife method [previous technique] = phenohcs, and poly-imine (p〇lyimide J搂 high _ sex and other characteristics, but its shortcoming is that the molecular chain ring material is often prone to delamination after impact ( The current use of delaminati〇n) is extremely high. Therefore, the development of high-, high-strength, high-temperature-resistant complex δ materials is improved. It is resistant to delamination and has become a composite material for high-performance sports equipment and aerospace industrial main structural parts. Important performance requirements. Evaluate the g-size of composites, mainly due to interlaminar fracture toughness of materials (interlaminar

Toughness) and / or compression strength after impact (c〇 ress 纣 纣 after after after after after after after after after after after after after after after after after after after after after after after after after after after after after after after after after after after after after after after after after after after after after after The specification is the compressive strength test of the constituent materials in the subsequent impact of 1500in-lb/in impact, and the quantity value is the CAI value. In the conventional method of strengthening the toughness of composite materials, the toughening thermosetting epoxy resin system is used. Generally, a carbon fiber or glass fiber reinforced DGEBA (diglycidyl ether of bisphenol A) / Dicy epoxy resin system, or TGDDM (tetraglycidyl 4, 4, -diaminodiphenyl methane) / DDS (diaminodiphenyl sulphone) epoxy resin composite material, The resin system is modified by elastomer (eg, CTBN (carboxyl terminated butadiene-acrylo-nitrile copoly- mer) liquid rubber], and the fracture toughness is significantly higher than that of the unblended modifier; The barrier effect of delamination damage between materials is limited, and the temperature resistance of the material is also 6 1247775.

In order to maintain the mechanical properties (such as tensile strength and modulus of elasticity) and the temperature (such as 'glass transition temperature (Tg)) of the bladed thermosetting resin material, experts and scholars also adopt high mechanical properties and resistance. Temperature-performance thermoplastic resins (eg, polyethersulfone, polysulfone, and polyetherimide) are blended or mixed in a thermosetting resin substrate to carry out toughening modification studies of the composite material, however, the degree of toughness of the high crosslinking degree thermosetting resin is deteriorated and Not as expected. The laboratory has also used the above thermoplastic resin to be blended into a high cross-linking epoxy resin to form a mixed resin, which is used as a resin substrate bonded to both sides of the reinforcing fiber to carry out toughening research of the composite material, and the result is CAI. The value increase rate is below 35%. ^ Interleaves toughening method to modify thermosetting resin laminate material is also one of the most effective ways to improve the toughness of composite materials. An appropriate layer of toughened resin may be placed between the layers of the laminated material. Once the material is impacted, the impact energy may be absorbed, so that the laminated material will not be damaged immediately after impact, and the composite material will be formed. The effect, this is called ^ $= method. Interlayering _ technology can be used in low modulus (mQdulus) resin or processed with thermoplastic resin into a film interlayer between the layers ^

Prepreg ', surface' as a layer, job material = plastic: or inorganic matter. (4) _ method can improve the high-performance composite early blade ... and its original temperature resistance and mechanical properties affect the seller: shirt The processing of the miscellaneous shape of the structural parts is not good (10). The solvent resistance of the structural parts that are easy to maintain and disintegrate will be deteriorated, and the limitation of the straight line is limited. Therefore, the problem of the female increase and decrease to avoid riding into the text to the phase is to be overcome. For example: need to add dusting or spraying = force,: 7 1247775 iiif layer uniformity is not easy to control, environmental pollution, complex mass production process, and pre-/texture surface adhesion is not good, is not conducive to lamination processing. Contents] The purpose of the month is to blend the thermosetting pure resin substrate with the principle and method of interlayer toughening by using the southern molecular powder blending modified thermosetting resin soil (temperature resistance can be above 16 °C). The high-temperature and high-toughness composite material of the polymer powder is prepared by laminating the prepreg of the fiber-to-face.

Therefore, in view of the problems of the prior art, the present invention provides a high-toughness composite=, comprising a core (four)-career material, which has a thief-dimensional material, and is bonded to the first side of the j-strong fiber. a thermosetting hybrid resin substrate bonded to the second side of the reinforcing fiber, and the thermosetting mixed resin substrate comprises a molecular powder blended therein, and the first prepreg is sequentially thermosetting a matt substrate and thermosetting The mixed resin substrates are superposed on each other to form a high-quality composite material.

The present invention also provides a method for producing a high-toughness composite material, comprising the following steps: First, preparing a thermosetting pure resin substrate and a thermosetting hybrid resin substrate separately from the first side and the second side of the reinforcing fiber a first prepreg, and the thermosetting hybrid resin substrate comprises a polymer powder blended therein; however, these first prepregs are sequentially combined with a thermosetting pure resin substrate and a thermosetting resin base. The materials overlap each other to form a high tenacity composite. The details and the technology of the present invention are described with reference to the drawings. [Embodiment] Referring to Figure 1, the manufacturing process of the high-altitude composite material provided by the present invention mainly comprises the following steps: First, pre-dip Material preparation (step 100): preparing a thermosetting pure resin and thermosetting mixed resin substrate (step cutting), and then combining the thermosetting pure tree sorghum substrate, the thermosetting mixed resin substrate and the reinforcing fiber to make a plurality of prepregs ( Step 120); Next, the high 8 1247775 toughness composite is completed by sequentially laminating the prepregs (step 200). The material and the composition of the composite material provided by the distribution of the singularity of the singularity of the squid, the thermosetting pure resin substrate used for the hardening agent is a ring containing a hardener, and the sputum is a sub-powder for nylon (polyamides). Polymer) The end of the 'reinforcing fiber is a carbon fiber bundle. 1. Prepreg preparation (Step 1〇〇)··· Preparation of thermosetting pure resin substrate and mixed resin substrate (Step 11〇):

^ The nylon powder was baked in an oven at 130 ° C for more than 1 hour, which was 2 ° ° C. A thermosetting hybrid resin substrate of a matured epoxy resin system and a thermosetting hybrid resin substrate of a nylon powder/200 t matured epoxy resin system (a blending weight ratio of nylon powder to epoxy resin of about 45:55) They are respectively placed in the resin tank of the film-making machine, and the temperature in the tank is 80~l〇〇°C, and the thin film-like pure resin substrate adhered to the release paper is respectively produced by the thicker control and the appropriate release paper pulling. In the mixed resin substrate, the area weight of the resin film (that is, the weight per unit area) is 50 to 60 g/m 2 and 20 to 30 g/m 2 , respectively. In the examples, the nylon powder is controlled in the range of Ιμιη~2〇μηι, and its weight content is about 1 to 4.5% for the prepreg.

b. Preparation of a plurality of prepregs (step 12A): This example is a prepreg production using a 100 cm wide production hot melt prepreg. The film-form thermosetting pure resin substrate and the thermosetting mixed resin substrate are respectively impregnated into the carbon fiber by using the prepreg of this type, and the upper layer portion of the prepreg is a thermosetting mixed resin substrate, and the lower portion is a thermosetting pure resin base. The prepreg resin content is 36 ± 2 wt ° / 〇. 2. Stack the prepreg to complete the high tenacity composite (step 2〇〇):

As shown in Fig. 2, a schematic view of the high tenacity composite material of the present embodiment. The upper layer portions (mixed resin substrates 15, 25) of the prepregs 10, 20 are directed upward, and the lower layer portions (pure resin substrates 11, 21) are faced downward, depending on (+45 〇 / 0 〇 / -45 〇 / 90 〇) 4S 9 1247775 1 _ Measure the lake test piece), and ride the top of the yoke, the second $ 'that is the original upper part (mixed resin substrate 31) toward: its ft (resin substrate 35) upwards The method is superposed on the mixed tree matte substrate 25 such that the outermost portion of the high tenacity composite material is pure tree wire. Therefore, the shouting composite material is composed of a purely fat base material, a carbon fiber 13, a mixed substrate 15, a pure resin substrate, a carbon fiber 23, a mixed resin substrate 25, a mixed resin substrate 31, and carbon fiber. 33. Pure resin substrate 35. ' Reference Table 1 and Table 2 are the test data of the composite material of the high tenacity composite material and the unblended molecular powder of the present embodiment. Table 1 Powder Content (Wt%) Tg (°C) CAI Value (ksi) Toughening Rate (%) 0 (Pure Resin) 216 15.0 — 3.5 (This Example) 211 30.0 100 Table 2 Test Items Pure Resin This Implementation Example Loss rate 0° Tensile strength (ksi) 0° Bending strength 312 309 1.0% 177 (ksi) 175 1.1% Compressive strength (ksi) 145 141 2.1% Note: The test piece of Table 2 belongs to 〇. The composite test piece obtained by lamination is arranged. 1247775 This high-toughness composite material is tested according to BSS 7260-96 (Boeing Standard Specification). The test piece is first impacted by the drop hammer impact tester and then subjected to the compression residual strength test using the universal testing machine. It is known that the increase rate can reach 100%, and the data through the glass transition temperature test shows that in the present embodiment. The blending of the dragon powder has little effect on the glass transition temperature of the composite, and only decreases by 5 °C. In addition, the compressive strength (test piece fabrication and testing according to ASTM D695-96 specification), bending properties (test strips according to ASTM D790-96), and tensile properties (tested according to ASTM D3039-96) The test results of the film system and the "test" show that the effect on the mechanical properties is not obvious, and the tensile strength is strong.

The damage rate of the degree and the bending strength are both below L 1%, and the reduction rate of the compressive strength is 2.7%. 'In the second embodiment, in order to make the outermost part of the high-toughness composite material a thermosetting pure grease substrate, the uppermost prepreg is reversely laminated to overlap, however, The uppermost prepreg is replaced by a prepreg which is combined with a carbon g by a thermosetting pure resin substrate.

The prepreg is produced in the same manner as the prepreg in the first embodiment (step 100). Only when the material is prepared, the pure resin substrate of the pie thief is impregnated into the carbon fiber to prepare the prepreg. For the dip, the prepreg resin content is 36 + 2 wt%. The prepreg is then superposed. - As shown in Fig. 3, the sound and diagram of the high tenacity composite material of the present embodiment. The position (4) of the superposition method is first to be closed: fat base 4〇 '5 ° 曰 wide material. 45, 55) upward, the lower part (pure resin substrate 41, 51; > downward, according to (+45 /0 /-45./90.) 4S quasi-equal arrangement of laminated square Laminated 'composite 32 layers (for CAI test pieces), and will be made of pure = f ^ carbon = _ _ red material (9) # 魏 合 resin substrate bb to make this high toughness composite Pure resin substrate. Therefore, the hybrid composite (4) is 12 11 1247775 substrate 41, carbon fiber 43, mixed resin substrate 45, pure resin substrate 51, carbon fiber 53, mixed resin substrate 55, pure resin Substrate 61, carbon fiber 63, and pure resin substrate 65. Example 3

The high tenacity composite material of this embodiment is produced in the same manner as in the first embodiment. Only the thermosetting pure resin substrate used in this embodiment is a 125 C curing grade epoxy resin system containing a hardener. The resin bath temperature of the film is 65 to 75, and the resin content of the prepreg is 38±2 wt0/ Hey. Referring to Table 3 and Table 4, the high toughness composite material obtained in the present embodiment is also obtained.

The physical and mechanical properties of the composites with and without blended polymer powders were tested and compared.

Tg (°C) Powder content (wt%) (Pure tree month 3·5 (this example) 138 136 CAI value (ksi) Toughening rate (%) 19· 35.0 84 Table 4 Pure resin I I η29.0 114

Test project

--- 丨丨丨„1丨 single point bending force (kgf) curvature (kgf) 29.4116 Μ contraction strength (ksi) 81.0 80.0 1.4%1.8% _also this high toughness composite according to BSS 7260-96 (Boeing Standard gauge,) Carry out the CAI test 'testing the test piece firstly after the drop hammer impact test machine drop hammer impact' and then use the universal testing machine for the compressive residual strength test, the increase of the knife rate can reach 1247775 8 peach, and via _ transfer Wenlang test data age, the domain powder material transfer temperature influence from, only reduce the sink. In addition, and by the two songs, three points to help the performance (using the golf club real test piece ': ^ -Μ

The data of Db95 96 gauge consumption test strip production and test shows that the influence of its properties is very limited. The single point bending performance and the three-point bending energy and the second rate are both f 1·8%, and the compression strength is degraded. The high-toughness composite material and the method thereof provided by the present invention are a high-toughness composite material and a method thereof, and the polymer powder is blended with the heat and tree silk material, and the wire and the method can be used. The effect of the Dahe touch composite material, the invention is not powder or spray-machine H, no environmental pollution problem, the powder coating layer is uniform, the production process is simple, and the surface of the prepared material still has its financial secrets. Conducive to the most f processing, and will not produce the good temperature and mechanical properties of its original composite; aside, * the examples show that the present invention has successfully established high performance, high temperature resistance (higher than 16 〇. High-mobility carbon fiber reinforced epoxy resin prepreg technology.

The preferred embodiments of the present invention are disclosed as described above, and are not intended to limit the scope of the invention, and may be modified and modified without departing from the spirit and scope of the invention. The scope of patent protection of the present invention is defined by the scope of the patent application attached to the specification. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart for producing a high-toughness composite material of the present invention; FIG. 2 is a schematic view showing a high-toughness composite material according to Embodiment 1 of the present invention; and FIG. 3 is a view of the present invention A schematic diagram of the high tenacity composite of Example 2. [Description of main component symbols] 10, 20, 30, 40, 50, 60 Prepreg 11 ' 2 Bu 35, 4 Bu 51, 6 Bu 65 Pure resin substrate 13, 23, 33, 43, 53, 63 Carbon fiber Μ ' 25 ' 31 ' 45, 55 mixed resin substrate 13 1247775 step 100 prepreg preparation step 110 preparing pure resin substrate and mixed resin substrate step 120 preparing a plurality of prepreg step 200 sequentially stacking the prepreg, To complete high toughness composites

14

Claims (1)

1247775 X. Patent Application Range: A TSJ initial composite material comprising: a plurality of first prepregs, each of the prepreg comprising: a reinforcing fiber having opposite sides - a side and a second side Γί 杂 pure tree wire, combined with the first _ two heat =, resin substrate, combined with the __ dimension of the month H New (four) molecular powder blended secret surface mixed tree 兮 m m some - Prepreg is sequentially mixed with the thermosetting pure resin substrate and ? The substrates are laminated to each other to form the high-dimension composite. The high-sensitivity composite material according to item 1, further comprising a first pre-material, which comprises: a surface; Reinforcing fiber having opposite-first side and second side; thermosetting pure resin substrate bonded to the first side of the reinforcing fiber a thermosetting hybrid substrate, the second side of the fine fiber comprising a reduced polymer powder blended in the whole oily mixed substrate; wherein the second prepreg is based on the thermosetting mixed resin base The material is laminated with the first prepreg hetero-solid mixed resin substrate, so that both sides of the high-weid edge composite material after lamination are the thermosetting pure resin substrate. 3. The high tenacity composite material according to claim 1, further comprising a second prepreg comprising: a reinforcing fiber having a first side and a second side; and a thermosetting property a pure resin substrate combined with the reinforcing fiber, wherein the first side and the second side of the reinforcing fiber are the thermosetting pure resin base 15 1247775; wherein the '4th prepreg system and the The thermosetting mixing of the prepreg: the resin substrate is superposed on the high-strength composite material, so that both sides of the high-motion composite material after lamination are the thermosetting pure resin substrate. 4. The high-reduction composite material according to claim 1, wherein the thermosetting pure resin substrate is an epoxy resin system. 5. If the scope of patent application is 帛1, the high-grade blade composite fiber is carbon fiber. π用灭6. The projecting composite material according to claim 1, wherein the molecular powder is a polyamide polymer powder. 1. If the application is to continue the combination of the first embodiment, the particle size of the high sub-powder is between Ιμιυ~2〇μιη. 8. If the application of the composite material as described in Item 1 is applied, the molecular weight of the molecular powder is between 1 and 4·5%. A method for producing a toughness composite material, comprising the steps of: preparing a plurality of first prepregs, each of the i-th dip material being a tamping pure tree, a substrate and a thermosetting mixed resin substrate Formed on the first side and the second side of a reinforcing fiber, respectively, and the thermosetting mixed tree a material comprising a plurality of polymer powders blended throughout the thermosetting hybrid resin substrate, and wherein the first prepreg sequentially closes the thermosetting pure resin substrate and the synthetic mixed resin substrate. The high tenacity composite is formed. #1,1〇· The manufacturing method of the high-vehicle edge-shaped composite material as described in claim 9 further includes a preparation-second prepreg which is made of _cure pure resin base And the thermosetting hybrid resin substrate are respectively bonded to a & face and a second side formed and the thermosetting hybrid resin is mixed with the plurality of polymer powders throughout the thermosetting hybrid resin, and the first The prepreg is laminated with the thermosetting hybrid resin substrate of the thermosetting hybrid substrate to form the high-dimensional ^ 1247775 composite material to make the high-toughness composite material two after lamination The outer side is the thermosetting pure resin substrate. 11. The method for producing a high-toughness composite material according to claim 9 of the patent application, further comprising: preparing a second prepreg which is composed of a thermosetting pure resin substrate and Forming a reinforcing fiber in combination, wherein the first side and the second side of the reinforcing fiber are both the thermosetting pure resin substrate, and the thermosetting property of the second prepreg and the first prepreg The high-resistance composite material is laminated on the mixed resin substrate, so that the high-strength composite material after the lamination is the thermosetting pure resin substrate. 12. The method of producing a high tenacity composite material according to claim 9, wherein the thermosetting pure resin substrate is formed of an epoxy resin system. The method for producing a high-toughness composite material according to claim 9, wherein the polymer powder is a polyamide polymer powder. 14. The method for producing a high-toughness composite material according to claim 9, wherein the polymer powder has a particle diameter of between 1 μm and 2 μm. 15. The weight content of the high molecular weight powders in the method of the high-killing composite material described in Item 9 of the application of the full-time division is between 1 and 4·5%. The method for producing a high-killing composite material according to item 9 of the i6m, wherein the reinforcing fiber is carbon fiber. 17