CN101331176A - Reinforced composite material - Google Patents
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- CN101331176A CN101331176A CNA2006800475540A CN200680047554A CN101331176A CN 101331176 A CN101331176 A CN 101331176A CN A2006800475540 A CNA2006800475540 A CN A2006800475540A CN 200680047554 A CN200680047554 A CN 200680047554A CN 101331176 A CN101331176 A CN 101331176A
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Abstract
The present invention relates to a reinforced composite material and a method for its production. The composite material comprises at least one cured resin having a reinforcing material. Preferably the reinforcing material is a plurality of glass fibres which are treated such that the properties of the interphase substantially surrounding each fibre are substantially equivalent to those of the bulk cured resin. The fibre treatment may be selected from the group consisting of a polymeric coating, a hydrophilic surface coating, a surface coating of a free radical inhibitor, or a reduction in the total surface area of the fibres. The reinforced composite material of the invention provides improved long-term mechanical properties compared to traditional glass fibre reinforced materials.
Description
Technical field
The present invention relates to reinforced composite, and particularly, relate to fiber reinforced polymer composites.Yet, be to be understood that to the invention is not restricted to this concrete Application Areas.
Background technology
Any discussion of the prior art in whole specification sheets should be considered to never admit that this prior art is extensively known, perhaps is formed in the part of the common sense in this field.
Fiber reinforced polymer composites is well known in the art, and prepares by curable resin and reactive diluent are reacted in the presence of radical initiator usually.Usually, curable resin is a unsaturated polyester resin, and reactive diluent is a vinyl monomer.Usually in prescription, comprise strongthener such as glass fibre so that dimensional stability and toughness to be provided.This reinforced composite is used for the industrial application of many keys, comprises building, automobile, aerospace, sea-freight and corrosion resistant products.
For the glass fibre reinforced polymer composites of routine, staple length is extremely assigned in tens of meters the scope in for example situation of heater supply winding at about 12mm usually.In these glass fibre polymer composites, most of fiber is fixed in position by mechanical friction, and fiber has only more weak combining with resin matrix.Therefore, the performance of these polymer composites mainly ascribes the length of used fiber to, and in these matrix materials, has discontinuous/gap between fiber and resin.The crackle that causes in resin matrix is found to be difficult to jump gaps, and therefore, in these matrix materials, the crackle that causes in resin stops at resin boundary usually, and does not arrive glass surface.Yet conventional glass fiber compound material has many shortcomings.For example, be difficult to before solidifying with resin " wetting " fiber, and even the dispersion of macrofiber in whole matrix material be difficult, particularly for complex component.
In addition, the glass reinforced polymer composites of this routine is subjected to their the common restriction that needs manual stratified production technology, and is perhaps very restricted aspect the shape of mould and complicacy.
In order to overcome these shortcomings, can use very short glass fibre.VSFPLC or very short fibre polymerisable liquid composites can be made tensile strength greater than 80MPa, the flexural strength layered product greater than 130MPa.VSFPLC is the very short surface-treated fortifying fibre and the suspension of polymerizing resin/thermoset such as UP resin, vinyl functional resins, Resins, epoxy or urethane resin.It is very short that the length of fiber is held, and making them not make liquid viscosity increase to the resin fibre mixture no longer is can spray or pumpable degree.VSFPLC can be used for using the fiberglass that replaces standard at open and closed molding and arrange (layout), and can be used as the substitute of thermoplastics in resin injection molding and rotational molding application.
Yet, needing the improvement that combines the aspect of fiber and matrix usually, can not be mechanically " keyed in the matrix because these very short glass fibre are too short.Use coupling agent to apply the raising that fortifying fibre can provide fiber and matrix bond aspect.For example, normally used a kind of coupling agent is DowCorning Z-6030, and it is the difunctional silane that contains methacrylate reactive organic group and 3 methoxy methyl silylation.Dow Corning Z-6030 and organic thermosetting resin and inorganic materials such as glass fibre react.Though these coupling agents can improve combining of fiber and matrix, the practicality of enhanced polymer composites is restricted, the embrittlement because they are easy in time.Sometimes need to have bigger flexible and flexible product.
In PCT patent application PCT/AU01/01484 (international publication WO 02/40577), attempted solving some such shortcomings, wherein before the coated glass fortifying fibre, made the coupling agent pre-polymerization with " plasticizing interface ".Being intended that of the coupling agent of pre-polymerization provides the rubber-like intermediate phase between fiber and matrix resin, thereby produces the product of shock resistance and intensity with raising.Yet under the situation of above-mentioned PCT, long-term embrittlement remains problem.In very short fibre polymerisable liquid composites, between fiber and resin, there is not the clearance.In VSFPLC, resin is attached on the resin matrix with chemical mode, and very close to each other between resin and fiber.The crackle direct extension that causes in resin matrix is to fiber surface.The point of the concentration of energy of the crackle that all spread on glass fibre, and energy is enough to make fiber to split.Can on the surface of fracture of the fiber of silane treatment, see a large amount of this evidences.For having especially like this greater than the layered product of the flexural strength of 100MPa.
An object of the present invention is to overcome or improve at least one in the shortcoming of above-mentioned prior art or a kind of useful substitute is provided.
Summary of the invention
According to first aspect, the invention provides a kind of method that is used to prepare reinforced composite, described method comprises: with at least a curable resin and the combination of Duo Gen fortifying fibre; And at least a curable resin is solidified, the cured resin of contiguous fortifying fibre limits intermediate phase, wherein handles fortifying fibre and makes the performance of intermediate phase be substantially equal to the performance of main body cured resin.
In a preferred embodiment, fortifying fibre is to have the glass fibre that is coupled to top coupling agent.Glass fibre can be selected from E-, S-or C-level glass.Glass fibre length is usually between about 100 and 1000 microns, and fiber preferably is dispersed in the whole resin.Coupling agent comprises multiple molecule, and every kind of molecule has that to be adapted to be incorporated into first on the glass fibre terminal and be adapted to be incorporated into second end on the resin when solidifying.Preferably, coupling agent is Dow Corning Z-6030.Yet, can use other coupling agent, as Dow Corning Z-6032 and Z-6075.Similarly coupling agent can be available from De Gussa and Crompton Specialties.
The performance of intermediate phase that is substantially equal to the performance of matrix resin can be to be selected from intensity, toughness and brittle mechanical property.As selecting or in addition, described performance can be physics or the chemical property that is selected from density, cross-linking density, molecular weight, chemical resistant properties and degree of crystallinity.
One or more curable resins preferably include polymkeric substance, and selected to have predetermined performance, comprise in tear strength, intensity, toughness and the resistance to embrittlement of raising one or more.Preferably, select resin to make under its solid state, the standard flex that is about the sample that 100mm is long, 15mm is wide and 5mm is thick according to size is tested, and it has the flexural toughness greater than 3 joules.Ideally, after preparation as long as five years in, the cured resin with this polymkeric substance has the flexural toughness greater than 3 joules.
In preferred embodiments, cured resin has resistibility to fracture propagation.Preferred cured resin can capacity supply fine-fibered and is had enough intrinsic tensile strengths stablize the minute crack district before the crackle, thereby limits or prevent spreading of crackle.Ideally, before it may reach the surface of glass fibre, the curable resin of polymer modification stoped crackle, if perhaps the minute crack in the crackle front arrives glass, then its energy shortage of having so that fiberglass surfacing break.The resin of these malleableizes is ideally suited the extremely short fiber reinforced composite materials.In addition, these resins provide the embrittlement along with aging appearance of reduction.Attention: since between the surface of glass fibre and fiber glass body big different rate of cooling, the real surface of glass fibre is far away from the intensity of fiber itself.This surface is easy to rupture.For this point is described, only need check the method that is used for preparation " (gluechipped) of gummed fragment " ambetti panel.
The processing that is used for fiber preferably reduces the catalytic processing at the resin polymerization of intermediate phase.In one embodiment, the processing that is used for fortifying fibre is the coating of polymeric coating.Preferably, the polymkeric substance of polymeric coating is monomer deficiency (monomer that is less than about 33%w/w), only has a low activity unsaturated polyester resin of medium relatively unsaturated amount.Aptly, unsaturated polyester resin being mixed with is hydrophilic basically.
In another embodiment, the processing that is used for fortifying fibre is the coating of hydrophilic surface coating.Make coupling agent (coated glass fiber) and hydrophilizing agent reaction that the hydrophilic surface coating is provided.One preferred aspect in, react in the presence of catalyzer such as tributyl tin by making Dow Corning Z-6030 and trihydroxy-compound such as TriMethylolPropane(TMP) or tetrahydroxy compound such as tetramethylolmethane, hydrophilizing agent is provided.Use the abundant coated glass fortifying fibre of water-wetted surface coating, make that the fiber of modification is hydrophilic basically.
In aspect another of hydrophilic surface coating embodiment, the glass fibre that uses the further processing of emulsion to handle.Processing can just mix, yet, preferably compound.Emulsion preferably comprises 16.6 parts of water, 100 parts of acetone and 200 parts of polymkeric substance.Randomly, emulsion comprises free radical inhibitors, and it generally includes quinhydrones (HQ) or hindered amine.Polymkeric substance can be a vinyl ester resin, yet, the preferred polymkeric substance of mentioning in the above.Particularly, this polymkeric substance is the low activity unsaturated polyester resin that only has medium relatively unsaturated amount of monomer deficiency (monomer that is less than about 33%w/w).Aptly, unsaturated polyester resin being mixed with is hydrophilic basically.
In another embodiment, the processing that fortifying fibre is used is to apply free radical inhibitors, as the coating of quinhydrones Acetyl Acetone, hindered phenol or hindered amine.In another embodiment, the processing that fortifying fibre is used is the total surface area that reduces fortifying fibre.
As mentioned above, very the polymerizable liquid matrix material of staple fibre need use coupling agent to improve combining of fiber and matrix usually, can not imbed in the matrix by machinery because fiber is too short.The applicant has been found that the use of these coupling agents trends towards causing reinforced composite embrittlement along with the time.Other people have attempted by using at least a resin is that the resin blend of " rubber-like " alleviates this embrittlement.For example disclosed in WO 02/40577, other selection is so that " rubber-like " phase to be provided around fiber with coupling agent modified.The present invention adopts diverse method.
Although be reluctant to arrest, it is believed that the prior art coupling agent that is coated on the glass fibre plays the resin polymerization in the catalysis intermediate phase zone of glass fibre direct neighbor (promptly with), thereby form the intermediate phase that becomes fragile in time in theory.Method of the present invention is with chemical mode " passivation " coupling agent coating, may be thereby attempt alleviating coupling agent to any influence of fiber-resin intermediate phase, and allow intermediate phase to have the performance that equates basically with the performance of main body cured resin.Yet should be appreciated that as the technician that the degree of passivation should be enough to alleviate coupling agent may be to any influence of fiber-resin intermediate phase, still realizes fully combining of fiber and matrix resin simultaneously.
The applicant has been found that, some provides a kind of reinforced composite surprisingly the present invention who opposes fully with prior art, described reinforced composite shows the embrittlement that reduces relatively than prior art glass reinforced composite, keep such as intensity the performance of toughness and heat-drawn wire simultaneously.Particularly, use the long-term embrittlement problem of the prior art matrix material of link coupled fiber significantly to be reduced.
According to second aspect, the invention provides a kind of reinforced composite, described reinforced composite comprises: at least a cured resin with many fortifying fibres, the cured resin of contiguous fortifying fibre limits intermediate phase, and described intermediate phase has the performance that equates basically with the performance of main body cured resin.
According to the third aspect, the invention provides a kind of method that is used for handling the fortifying fibre that uses at the matrix material that comprises curable resin, described method comprises the following steps: in polymeric coating, hydrophilic surface coating or the free radical inhibitors coating one or more are coated on the fortifying fibre, make in use, the cured resin of contiguous fortifying fibre limits intermediate phase, and described intermediate phase has the performance that equates basically with the performance of main body cured resin.
According to fourth aspect, the invention provides a kind of fortifying fibre that is used to comprise the matrix material of curable resin, be coated with in polymeric coating, hydrophilic surface coating or the free radical inhibitors coating one or more on the described fortifying fibre, make in use, the cured resin of contiguous fortifying fibre limits intermediate phase, and described intermediate phase has the performance that equates basically with the performance of main body cured resin.
According to the 5th aspect, the invention provides a kind of method that is used for reducing the degradation property of matrix material, described matrix material has curable resin and Duo Gen and is scattered in wherein fortifying fibre, the cured resin of contiguous fortifying fibre limits intermediate phase, described method comprises the following steps: to reduce the total surface area of fortifying fibre, thereby the reduction of the amount of corresponding intermediate phase is provided.
According to the 6th aspect, the invention provides a kind of moulded composite body according to a first aspect of the invention.
According to the 7th aspect, the invention provides a kind of fortifying fibre of processing according to a third aspect of the invention we.
According to eight aspect, the invention provides a kind of method that is used for molded composites, described method comprises the following steps: to provide at least a curable resin and Duo Gen the mixture according to the fortifying fibre of fourth aspect; Described mixture is applied in the mould; And described at least a curable resin is solidified.
According to the 9th aspect, the invention provides a kind of by matrix material according to the molding of the method for eight aspect preparation.
According to the tenth aspect, the invention provides a kind of liquid curing matrix material, it comprises at least a curable resin and Duo Gen fortifying fibre, make in use, the cured resin of contiguous described fortifying fibre limits intermediate phase, and the processed performance of described intermediate phase that makes of wherein said fortifying fibre is substantially equal to the performance of main body cured resin.
According to the tenth on the one hand, the invention provides a kind of liquid curing matrix material, it comprises at least a curable resin and Duo Gen fortifying fibre, be coated with in polymeric coating, hydrophilic surface coating or the free radical inhibitors coating one or more on the described fortifying fibre, make when solidifying, the cured resin of contiguous described fortifying fibre limits intermediate phase, and described intermediate phase has the performance that equates basically with the performance of main body cured resin.
Unless context is requirement clearly in addition, otherwise in whole specification sheets and claims, speech ' comprise ', ' comprise ' etc. should be interpreted into and the exclusive or exhaustive adversative meaning that comprises; That is, the meaning is " including but not limited to ".
When pointing out in an embodiment or in addition, all numerical value that are illustrated in the amount of this used composition or reaction conditions are to be understood as in all cases all by term " pact " and modify.Embodiment is not intended to and limits the scope of the invention.Below, when perhaps pointing out in addition, " % " refers to " weight % ", and " ratio " refers to " weight ratio ", and " part " refers to " weight part ".
In description and claimed the present invention, following term will be used according to the definition of stating below.It should also be understood that in this used term purpose only to be to describe specific embodiments of the present invention, is restrictive and be not intended to.
In whole specification sheets, term adopts " fiber " and " plurality of fibers " to comprise small pieces and a plurality of small pieces respectively.Glass fibre is for the optimal fiber of the present invention.Yet, under the situation that does not depart from scope of the present invention, can use other mineral fibre, as wollastonite, and ceramic fiber.
In whole specification sheets, adopt term " performance " and " multiple performance " to comprise typical machinery, physics and the chemical property of polymkeric substance and cured resin.For example, mechanical property is to be selected from flexible and/or tensile strength, toughness, elasticity, plasticity, the performance in ductility, fragility and the shock strength.Chemistry and/or physicals are those performances that are selected from density, hardness, cross-linking density, molecular weight, chemical resistant properties and the degree of crystallinity.
In whole specification sheets, adopt term " catalysis (the catalyse) " term relevant with radical polymerization " to cause (initiate) " and " causing (initiation) " synonym with " catalysis (catalysation) ".
It should also be understood that in this application term " material " refers to the fibre/of liquid and solid form.Described material itself can be to provide with cured form, uncured liquid form or as the component of separating (fortifying fibre and the resin that for example are used for field mix independently).
Embodiment
The invention provides a kind of be used to the prepare method of reinforced composite and the composite bodies for preparing by this method.Described method comprises the following steps: to make fiber be dispersed in basically in the whole resin at least a curable resin and many fortifying fibre combinations, and makes resin solidification.Preferably, described resin is to have about 40% reactive diluent, as the vinyl ester resin of styrene monomer.Yet, can also use other component, as single-and two-and three-functional acrylate and methacrylic ester.As selection, described resin can be selected from unsaturated polyester resin, epoxy vinyl ester resin, vinyl functional resins, tough and tensile vinyl functional urethane resin, tough and tensile vinyl functional acrylic resinoid and flexible vibrin of non-plastifying and their combination.
In preferred embodiments, described fiber is to be selected from E-, the S-of length between about 100 and 1000 microns and the glass fibre of C-level glass.Yet, can also use length greater than 1000 microns fiber.Preferably, with its with one or more coupling agent treatment before, remove any sizing agent from glass fibre.Preferred coupling agent is Dow Corning Z-6030.Yet, can use other coupling agent, as Dow Corning Z-6032 and Z-6075.
Described at least a curable resin can comprise polymkeric substance, selected or by this polymer modification with one or more the pre-determined characteristics in tear strength, intensity, toughness and the resistance to embrittlement with the raising of being selected from.Preferably, for size be about that 110mm is long, 15mm is wide and 5mm is thick, through the sample of standard flex test, after preparation as long as five years in, the cured resin of polymer modification has the flexural toughness greater than 3 joules.
In preferred embodiments, the curable resin of polymer modification is resistive to spreading of crackle.These polymer modification resins provide the embrittlement that occurs along with wearing out of reduction.Preferably, described polymkeric substance is monomer deficiency (monomer that is less than about 33%w/w), only has a low activity unsaturated polyester resin of medium relatively unsaturated amount.The example of these polyester is provided in the following table.Aptly, these polyester are hydrophilic.
In case resin solidification and reinforced composite is provided, be close to and surround basically the cured resin qualification intermediate phase of each root fiberglass reinforcement, and fortifying fibre processed performance of intermediate phase that makes before their add curable resin is substantially equal to the performance of main body cured resin.In one embodiment, the processing that fiber is used is a polymer-coated.The preferably above-mentioned low activity unsaturated polyester resin of the polymkeric substance of polymeric coating.
As mentioned above, although be reluctant to arrest in theory, the applicant thinks that the fiber of use prior art coupling agent treatment plays the catalytic resin polymerization, thereby forms the intermediate phase that has with the remarkable different performance of main body cured resin.Intermediate phase with highly cross-linked material will have the performance that is different from matrix resin greatly, thereby influence the machinery and the physicals of final cured reinforced composite body.For example, it is more crisp than matrix resin in itself to have an intermediate phase of highly cross-linked material.In rupture process, the crackle that spreads will be easier to make this fragility intermediate phase fracture, and any cracking resistance line performance of the resin in intermediate phase will significantly reduce.In addition, should be appreciated that as the technician fiber that uses is many more in composite bodies, the total amount of the fragility intermediate phase of generation is big more, and composite bodies becomes more crisp.
By handling the link coupled glass fibre to reduce the catalysis of radical polymerization, the applicant can reduce the influence of link coupled glass fibre to intermediate phase, makes intermediate phase have and main body cured resin similar performance.In other embodiments, use the surface of the coating processing glass fibre of one or more free radical inhibitors such as quinhydrones or Acetyl Acetone, hindered phenol and hindered amine.The coating of one or more free radical inhibitors and the surface association of glass fibre, being reduced in the catalysis of the resin polymerization in the intermediate phase, and described intermediate phase has and main body cured resin similar performance.
In another embodiment, described processing is the total surface area that reduces fiber.For example, this can be by replacing glass fibre to realize with having larger-diameter glass fibre.Be noted that the glass fibre that is generally used for glass fibre reinforced composion has the diameter between about 5-12 micron.Yet, the applicant finds the final performance for reinforced composite body, the glass fibre that use has the diameter between about 15-24 micron provides significantly few embrittlement, and reason is the glass fibre for given weight, and the increase of total surface area and Fibre diameter is inversely proportional to.Certainly, can use diameter even 24 microns bigger fibers of ratio, yet, there is actual manufacturing limit in fibre property.
In this embodiment, though glass surface still can the catalytic resin polymerization to produce the fragility intermediate phase, the total amount of brittle interphase material reduces relatively.In addition, for the final cured polymer matrix material with similar mechanical property is provided, the length of used larger-diameter glass fibre preferably is longer than the length that is generally used for than the fiber of minor diameter.
Should recognize as the technician, can also use the combination of above-mentioned embodiment in due course.For example, should use and have larger-diameter glass fibre and use free radical inhibitors coated fiber or use aforesaid polymer-coated fiber.
In further embodiment, processing comprises two-step approach, wherein at first uses the first reagent coated glass fiber, makes second reagent and first reagent react so that the glass fibre of hydrophilic surface modification basically to be provided then.Preferably, first reagent be have be fit to terminal and when solidifying, be fit to coupling agent with second reagent or resin-bonded with fiber bonded first.In a preferred embodiment, coupling agent is methacryloxypropyl trimethoxy silane (Dow Corning Z-6030).Second reagent is included in the reaction product between first reagent and trihydroxy-compound such as the TriMethylolPropane(TMP).Yet in embodiment optionally, oxy-compound is tetrahydroxy compound such as tetramethylolmethane.The reaction of Z-6030 and TriMethylolPropane(TMP) is in the presence of tin catalyst such as the tributyl tin, carry out under the reaction conditions that is fit to.
The method of handling glass fibre according to before embodiment also comprises mixes coated fortifying fibre or the compound step with emulsion.Described emulsion preferably comprises: 16.6 parts of water, 100 parts of acetone and 200 parts of polymkeric substance, the wherein preferably above-mentioned wetting ability low activity of this polymkeric substance unsaturated polyester resin.Described emulsion can also comprise wetting ability free radical inhibitors such as HQ.
Embodiment
Describe the present invention referring now to the following example, described embodiment should all be considered to illustrative in all fields and be nonrestrictive.
Use hydrophilic surface coating to handle glass fibre
1. the E-glass fibre is cut to 3400 microns average fiber length, is milled to 700 microns mean length then.
2. use boiling water and potent washing composition and under powerful condition of stirring, clean the ground glass fibre.Then washing composition is rinsed from fiber.
3. the methacryloxy Trimethoxy silane (Dow Z-6030) with 1%w/w is suspended in the water of pH 4, and fiber is added in the suspension.With the mixture that obtains vigorous stirring 60 minutes at room temperature.
4. liquid pours off from glass fibre then, makes their still mixed things wetting.
5. the fiber that in pH is 7 water, disperses Z-6030-to handle once more then.
6. individually, in the presence of tin catalyst (for example tributyl tin), make the solution of Z-6030 and TriMethylolPropane(TMP) (TMP) react 15-20 minute down to form the Z-6030-TMP adducts that viscosity is about 1200-1500cP at 110-120 ℃.In reaction process, emit methyl alcohol.
7. fiber and Z-6030-TMP adducts that Z-6030 is handled react so that the fiber of hydrophilic treatment to be provided.This is to add in the entry with the concentration of about 2-3wt% of fiber in water and with the Z-6030-TMP adducts by fiber dispersion that Z-6030 is handled to realize.With mixture stir about together 10 minutes.With fiber separation, centrifugal then then to remove excessive water.Then will " wetting " fiber from 30 ℃ of dry 3-4 hour beginnings, heating 5-7 minute between 110 and 125 ℃ then.
8. individually, preparation has the polymer emulsion of 200 parts of polymkeric substance, 100 parts of acetone and 16.6 parts of water.Preferably, described polymkeric substance is hydrophilic resin such as unsaturated polyester.
9. then that the fiber and the emulsifying resins of hydrophilic treatment is compound, disperse until quantitative and even with the emulsion of the fiber of about 93w/w% and 7w/w%.
10. then compound fiber-emulsion mixture is added in the base resin than 90-55% resin with about 10-45% fiber-emulsion.
Table 1 provides the flexural strength data of the curing transparent foundry goods (clear casts) of commercially available Derakane epoxy vinyl ester resin 411-350 (AshlandChemicals).These test boards prepare according to manufacturers specifications, and obtain modulus in flexure mean value, the surrender flexural stress mean value of about 120MPa and the elongation at break mean value between about 5 to 6% of about 3.1GPa.
Table 2 has shown with table 1 similar, but the test board of thermal ageing.By 108 ℃ of thermal treatments 2 hours, subsequently controlled chilling to be lower than 40 ℃ about 2 hours, with the plate thermal ageing.As seeing, in experimental error, the modulus in flexure after wearing out roughly is identical with flexural stress.Yet elongation at break roughly reduces by half, and represents the significantly embrittlement along with accelerated deterioration of described plate.
| Matrix material | Modulus in flexure (GPa) | Surrender flexural stress (MPa) | Elongation at break (%) |
| Test board 1 | 2.98 | 112 | 4.9 |
| Test board 2 | 3.12 | 119 | 5.7 |
| Test board 3 | 3.11 | 123 | 5.6 |
| Test board 4 | 3.28 | 132 | 6.0 |
The flexural strength data of the transparent foundry goods of curing (unaged) of table 1:Derakane 411-350 epoxy vinyl ester resin
| Matrix material | Modulus in flexure (GPa) | Surrender flexural stress (MPa) | Elongation at break (%) |
| Test board 5 | 3.30 | 117 | 3.0 |
| Test board 6 | 3.40 | 121 | 3.1 |
| Test board 7 | 3.10 | 131 | 4.1 |
| Test board 8 | 3.20 | 123 | 3.6 |
| Test board 9 | 3.20 | 127 | 4.2 |
The flexural strength data of the transparent foundry goods of aged of table 2:Derakane 411-350 epoxy vinyl ester resin
Table 3 provides the flexural strength data of the aged curing transparent foundry goods of the Derakane epoxy vinyl ester resin that is added with various polymkeric substance (following argumentation).As seeing, obtain the about 3.3GPa of modulus in flexure mean value, surrender about 135MPa of flexural stress mean value and the elongation at break mean value between about 5 to 7%.Compare elongation rate data between table 2 and 3, the interpolation of various polymkeric substance has significantly reduced aging embrittlement as can be seen.
| Matrix material | Modulus in flexure (GPa) | Surrender flexural stress (MPa) | Elongation at break (%) |
| Test board 10+ polymkeric substance 1 | 3.20 | 132 | 6.7 |
| Test board 11+ polymkeric substance 2 | 3.20 | 131 | 4.9 |
| Test board 12+ polymkeric substance 3 | 3.30 | 136 | 5.7 |
| Test board 13+ polymkeric substance 4 | 3.50 | 140 | 6.0 |
| Test board 14+ polymkeric substance 5 | 3.60 | 146 | 6.6 |
Table 3: the flexural strength data of the transparent foundry goods of aged with Derakane 411-350 epoxy vinyl ester resin of 12-15 weight % polymeric additive.
The polymkeric substance that provides in table is the condensation product of polyvalent alcohol and diprotic acid.Each polymkeric substance that comprises polyvalent alcohol and diprotic acid is provided in table 4.Usually dibasic alcohol by will being similar to equimolar amount and acid heat about 4 to about 12 hours surpassing about 200 ℃ temperature, prepare these polyester.Most of unsaturated be that form with the dimethyl ester base exists.These polyester have at about 15 acid numbers to about 25 the scope.(this acid number be in and the milligram number of the required potassium hydroxide of 1g sample).
3 liters of round-bottomed flasks are equipped with paddle stirrer, thermometer, inert gas entrance and outlet and electrically heated cover.Esterification divided for 2 stages carried out.Fs is that saturated acid is reacted in excess glycol, and subordinate phase is to carry out under the situation of the addition of unsaturated acid and residual dibasic alcohol.Between the described stage, reaction vessel is weighed, and add dibasic alcohol when needed to supply any loss.With between mixture heating up to 150 and 170 ℃, discharging water, and the condenser inlet temperature is higher than 95 ℃.
In ensuing 2-3 hour, the temperature of mixture is increased to 240 ℃.Mixture is cooled to 105 ℃ then, and with suppress the vinylbenzene blend.Final vibrin comprises the unsaturated polyester of 80 weight % and 20% vinylbenzene.
| Polymkeric substance | Polyvalent alcohol | Diprotic acid | The ratio of saturated acid and unsaturated acid |
| Polymkeric substance 1 | 4 moles of propylene glycol, 1.5 moles of MP-glycol | 2 moles of terephthalic acids, 1 mole of m-phthalic acid, 2 moles of fumaric acid | 3: 2 |
| Polymkeric substance 2 | 5.5 moles of glycol ethers | 3 moles of terephthalic acids, 2 moles of fumaric acid | 3: 2.And, when beginning, subordinate phase keeps the excessive glycol of 0.5M |
| Polymkeric substance 3 | 6 moles of glycol ethers, 1.5 moles of MP-glycol | 1,4-cyclohexane diacid, fumaric acid | 4: 3 |
| Polymkeric substance 4 and 7 | Nuplex 316/ Terephth 50/50 blend | ||
| Polymkeric substance 5 | 6.25 moles of neopentyl glycol, 2 moles of propylene glycol | 1,4.5 moles of 4-cyclohexane diacids, 3 moles of fumaric acid | 3: 2 |
| Polymkeric substance 6 | Glycol ether | 1,3 moles of 4-cyclohexane diacids, 2 moles of fumaric acid | 3: 2 |
| Polymkeric substance 8 | 6.25 moles of neopentyl glycol, 1 mole of propylene glycol | 1,4 moles of 4-cyclohexane diacids, 3 moles of fumaric acid | 4: 3 |
Table 4: be used for polyester in the modification of the Derakane of table 3 and 5 base resin.
Table 5 provides the flexural strength data of Derakane epoxy vinyl ester resin of the ratio (in bracket) of the resin/glass fiber with regulation, and wherein glass fibre is only to use the Z-6030 coupling agent treatment.
| Matrix material | Modulus in flexure (GPa) | Surrender flexural stress (MPa) | Elongation at break (%) |
| Test board 15 (2.3: 1) | 6.20 | 124 | 0.87 |
| Test board 16 (2: 1) | 6.70 | 129 | 0.70 |
| Test board 17 (1.9: 1) | 7.50 | 135 | 0.63 |
| Test board 18 (1.7: 1) | 8.10 | 142 | 0.60 |
| Test board 19 (1.6: 1) | 9.00 | 149 | 0.58 |
Table 5: the flexural strength data of the glass fibre that the aged Z-6030 in Derakane 411-350 epoxy vinyl ester resin handles.
Table 6 has shown the flexural strength data according to the aged test board of Derakane epoxy vinyl ester resin of the present invention, and described resin has the aforesaid polymeric additive of about 12-15 weight % and the glass fibre that 45-50 weight is handled.
| Matrix material | Modulus in flexure (GPa) | Surrender flexural stress (MPa) | Elongation at break (%) |
| Test board 20+ polymkeric substance 5 | 6.10 | 136 | 2.6 |
| Test board 21+ polymkeric substance 6 | 6.20 | 133 | 2.2 |
| Test board 22+ polymkeric substance 6 | 5.90 | 129 | 2.9 |
| Test board 23+ polymkeric substance 7 | 6.00 | 134 | 3.1 |
| Test board 24+ polymkeric substance 8 | 6.20 | 135 | 3.4 |
Table 6: according to the flexural strength data with Derakane 411-350 epoxy vinyl ester resin of the polymeric additive of 12-15 weight % and the glass fibre that 47 weight are handled of the present invention, wherein said processing comprises hydrophilic surface coating and emulsifying polymers.
In the comparison of the deflection data that provide in table 5 and table 6, test board 20-24 according to the present invention as can be seen has the elongation at break of the burn-in board that significantly improves, thereby the reduction of aging embrittlement is provided.
Table 7 provides the flexural strength data of ageing test plate of Derakane epoxy vinyl ester resin of the ratio (in bracket) of the resin/glass fiber with regulation, and wherein glass fibre is with the insufficient plastic resin treatment of monomer.Test board 25 is not coated, and plate 26 to 28 is coated.Plate with coated glass fibers has the toughness that significantly improves.
| Matrix material | Modulus in flexure (GPa) | Surrender flexural stress (MPa) | Elongation at break (%) |
| Test board 25 (2.3: 1) | 6.20 | 124 | 0.87 |
| Test board 26 (5: 1) | 3.80 | 120 | 4.0 |
| Test board 27 (5: 1) | 3.50 | 115 | 4.0 |
| Test board 28 (5: 1) | 3.60 | 118 | 4.0 |
Table 7: have the flexural strength data of ageing test plate of Derakane 411-350 epoxy vinyl ester resin of the glass of polymer treatment, wherein said polymkeric substance is the insufficient resin of monomer.
Industrial usability
The present invention can be used for multiple industry, comprising: building, automobile, aerospace, sea-freight and corrosion resistant products.Compare with the glass fibre reinforcement of routine, reinforced composite of the present invention provides the long-term mechanical properties of raising.
Although specifically described the present invention with reference to specific embodiment, those skilled in the art are to be understood that the present invention can implement with many other forms.
Claims (86)
1. method that is used to prepare reinforced composite, described method comprises: with at least a curable resin and the combination of Duo Gen fortifying fibre; And described at least a curable resin is solidified, the cured resin of contiguous described fortifying fibre limits intermediate phase, wherein handles described fortifying fibre and makes the performance of described intermediate phase be substantially equal to the performance of main body cured resin.
2. method that is used for handling the fortifying fibre that uses at the matrix material that comprises curable resin, described method comprises the following steps: in polymeric coating, hydrophilic surface coating or the free radical inhibitors coating one or more are coated on the described fortifying fibre, make in use, the cured resin of contiguous described fortifying fibre limits intermediate phase, and described intermediate phase has the performance that equates basically with the performance of main body cured resin.
3. according to the method for claim 1 or claim 2, described method comprises coupling agent is coupled to step on the described fortifying fibre.
4. according to the method for claim 3, wherein said coupling agent is the silane of vinyl functional.
5. according to the method for claim 4, wherein said coupling agent is selected from Dow Corning Z-6030, Z-6032 and Z-6075.
6. according to each method in preceding claim, wherein said fortifying fibre is a glass fibre.
7. according to the method for claim 6, the length of wherein said glass fibre is between about 100 and 1000 microns.
8. according to each method in preceding claim, wherein said performance comprises the mechanical property that is selected from intensity, toughness and fragility or their combination.
9. according to each method in preceding claim, wherein said performance comprises physics or the chemical property that is selected from density, cross-linking density, chemical resistant properties, molecular weight and degree of crystallinity or their combination.
10. according to each method in preceding claim, described method comprises polymkeric substance and the described at least a curable resin combination step with the resin of preparation polymer modification.
11., wherein described polymkeric substance and described at least a curable resin are made up between about 5 to 50%w/w according to the method for claim 10.
12. according to the method for claim 10 or claim 11, wherein said curable resin selected or by described polymer modification to have predetermined performance.
13. according to the method for claim 12, wherein said performance is selected from one or more in tear strength, intensity, toughness and the resistance to embrittlement.
14. according to each method in the claim 10 to 13, wherein when testing in the standard flex test, described cured resin has greater than about 3 joules flexural toughness, sample has the size of the thickness of the width of length, 15mm of about 100mm and 5mm.
15. according to the method for claim 14, wherein in as long as five years, described cured resin has the flexural toughness greater than 3 joules.
16. according to each method in the claim 10 to 15, wherein said polymkeric substance is the insufficient low activity unsaturated polyester resin of monomer.
17. according to the method for claim 16, the described monomer content of wherein said polymkeric substance is between about 5 to 30%w/w.
18. method according to claim 16 or claim 17, wherein by making polyvalent alcohol and acid-respons that described unsaturated polyester resin is provided, described polyvalent alcohol is selected from propylene glycol, methyl propanediol, neopentyl glycol and glycol ether, and wherein said acid is selected from terephthalic acid, m-phthalic acid, fumaric acid and 1,4-cyclohexane diacid, described unsaturated polyester resin are included in saturated acid and the unsaturated acid ratio between about 1.2: 1 to 2: 1.
19. according to each method in preceding claim, wherein said processing is the polymeric coating that is coated on the described fortifying fibre.
20. according to the method for claim 19, the described polymkeric substance of wherein said polymeric coating is the insufficient low activity unsaturated polyester resin of monomer.
21. according to each method in the claim 1 to 18, wherein said processing is that hydrophilic surface coating is coated on the described fortifying fibre.
22. according to the method for claim 21, wherein said hydrophilic surface coating prepares by making the reaction of methacryloxypropyl trimethoxy silane and TriMethylolPropane(TMP).
23. according to the method for claim 21 or claim 22, wherein said hydrophilic surface coating also comprises the processing of using emulsion.
24. according to the method for claim 23, wherein said emulsion comprises about 16.6 parts of water, 100 parts of acetone and 200 parts of polymkeric substance.
25. according to the method for claim 23 or claim 24, wherein said emulsion comprises free radical inhibitors.
26. according to the method for claim 25, wherein said free radical inhibitors is quinhydrones, hindered amine, Acetyl Acetone, hindered phenol or their combination.
27. according to each method in the claim 1 to 18, wherein said processing is that the free radical inhibitors coating is coated on the described fortifying fibre.
28. according to each method in the claim 10 to 27, wherein select identical polymkeric substance with:
A. with described curable resin modification; And/or
B. apply described fiber; And/or
C. be used to prepare described emulsion.
29. according to each method in the claim 1 to 18, wherein said processing is the total surface area that reduces described fortifying fibre.
30. according to the method for claim 29, the described reduction of wherein said surface-area is to provide by the size that changes described fortifying fibre.
31., wherein change described size by diameter that increases described fortifying fibre and/or the length that reduces described fortifying fibre according to the method for claim 30.
32. according to the method for claim 31, the diameter of wherein said fiber is between about 15 to 24 microns.
33. according to each method in preceding claim, the modulus in flexure of wherein said cured composite material is greater than about 3.5GPa.
34. according to each method in preceding claim, the flexural stress of wherein said cured composite material is greater than about 120MPa.
35. according to each method in preceding claim, the elongation at break of wherein said cured composite material is greater than about 2%.
36. according to each method in preceding claim, wherein when comparing with the fiber of not handling according to the present invention, described processing is reduced in the catalysis of the resin polymerization in the intermediate phase.
37. according to each method in preceding claim, wherein when comparing with the fiber of not handling according to the present invention, described processing reduces the embrittlement of described intermediate phase.
38., wherein described fiber fully is coupled on the described resin to strengthen described resin according to each method in preceding claim.
39. reinforced composite, described reinforced composite comprises: at least a cured resin with many fortifying fibres, the cured resin of contiguous described fortifying fibre limits intermediate phase, and described intermediate phase has the performance that equates basically with the performance of main body cured resin.
40. fortifying fibre that is used to comprise the matrix material of curable resin, be coated with in polymeric coating, hydrophilic surface coating or the free radical inhibitors coating one or more on the described fortifying fibre, make in use, the cured resin of contiguous described fortifying fibre limits intermediate phase, and described intermediate phase has the performance that equates basically with the performance of main body cured resin.
41. according to the reinforced composite of claim 39 or according to the fortifying fibre of claim 40, wherein said fortifying fibre has the coupling agent that is coupled on it.
42. according to the reinforced composite of claim 41 or according to the fortifying fibre of claim 41, wherein said coupling agent is the silane of vinyl functional.
43. according to the reinforced composite of claim 42 or according to the fortifying fibre of claim 42, wherein said coupling agent is selected from Dow Corning Z-6030, Z-6032 and Z-6075.
44. according in the claim 39 to 43 each reinforced composite or according to each fortifying fibre in the claim 40 to 43, wherein said fortifying fibre is a glass fibre.
45. according to the reinforced composite of claim 44 or according to the fortifying fibre of claim 44, the length of wherein said glass fibre is between about 100 and 1000 microns.
46. according in the claim 39 to 45 each reinforced composite or according to each fortifying fibre in the claim 40 to 45, wherein said performance comprises the mechanical property that is selected from intensity, toughness and fragility or their combination.
47. according in the claim 39 to 46 each reinforced composite or according to each fortifying fibre in the claim 40 to 46, wherein said performance also comprises physics or the chemical property that is selected from density, cross-linking density, chemical resistant properties, molecular weight and degree of crystallinity or their combination.
48. according in the claim 39 to 47 each reinforced composite or according to each fortifying fibre in the claim 40 to 47, wherein said at least a curable resin comprises the resin of polymkeric substance with the preparation polymer modification.
49., wherein comprise described polymkeric substance with the ratio between about 5 to 50%w/w according to the reinforced composite of claim 48 or according to the fortifying fibre of claim 48.
50. according to the reinforced composite of claim 48 or claim 49 or according to the fortifying fibre of claim 48 or claim 49, wherein said curable resin selected or by described polymer modification to have predetermined performance.
51. according to the reinforced composite of claim 50 or according to the fortifying fibre of claim 50, wherein said performance is selected from one or more in tear strength, intensity, toughness and the resistance to embrittlement.
52. according in the claim 48 to 51 each reinforced composite or according to each fortifying fibre in the claim 48 to 51, wherein, when in the standard flex test, testing, described cured resin has greater than about 3 joules flexural toughness, and sample has the size of the thickness of the width of length, 15mm of about 100mm and 5mm.
53. according to the reinforced composite of claim 52 or according to the fortifying fibre of claim 52, wherein in as long as five years, described cured resin has the flexural toughness greater than 3 joules.
54. according in the claim 48 to 53 each reinforced composite or according to each fortifying fibre in the claim 48 to 53, wherein said polymkeric substance is the insufficient low activity unsaturated polyester resin of monomer.
55. according to the reinforced composite of claim 54 or according to the fortifying fibre of claim 54, the described monomer content of wherein said polymkeric substance is between about 5 to 30%w/w.
56. according to the reinforced composite of claim 54 or claim 55 or according to the fortifying fibre of claim 54 or claim 55, wherein by making polyvalent alcohol and acid-respons that described unsaturated polyester resin is provided, described polyvalent alcohol is selected from propylene glycol, methyl propanediol, neopentyl glycol and glycol ether, and wherein said acid is selected from terephthalic acid, m-phthalic acid, fumaric acid and 1,4-cyclohexane diacid, described unsaturated polyester resin are included in saturated acid and the unsaturated acid ratio between about 1.2: 1 to 2: 1.
57. according in the claim 39 to 56 each reinforced composite or according to each fortifying fibre in the claim 40 to 56, wherein said processing is the polymeric coating that is coated on the described fortifying fibre.
58. according to the reinforced composite of claim 57 or according to the fortifying fibre of claim 57, the described polymkeric substance of wherein said polymeric coating is the insufficient low activity unsaturated polyester resin of monomer.
59. according in the claim 39 to 58 each reinforced composite or according to each fortifying fibre in the claim 40 to 58, wherein said processing is the hydrophilic surface coating that is coated on the described fortifying fibre.
60. according to the reinforced composite of claim 59 or according to the fortifying fibre of claim 59, wherein said hydrophilic surface coating prepares by making the reaction of methacryloxypropyl trimethoxy silane and TriMethylolPropane(TMP).
61. according to the reinforced composite of claim 59 or claim 60 or according to the fortifying fibre of claim 59 or claim 60, wherein said water-wetted surface applies and also comprises the processing of using emulsion.
62. according to the reinforced composite of claim 61 or according to the fortifying fibre of claim 61, wherein said emulsion comprises about 16.6 parts of water, 100 parts of acetone and 200 parts of polymkeric substance.
63. according to the reinforced composite of claim 61 or claim 62 or according to the fortifying fibre of claim 61 or claim 62, wherein said emulsion comprises free radical inhibitors.
64. according to the reinforced composite of claim 63 or according to the fortifying fibre of claim 63, wherein said free radical inhibitors is quinhydrones, hindered amine, Acetyl Acetone, hindered phenol or their combination.
65. according in the claim 39 to 56 each reinforced composite or according to each fortifying fibre in the claim 40 to 56, wherein said processing is the free radical inhibitors coating that is coated on the described fortifying fibre.
66. according in the claim 48 to 65 each reinforced composite or according to each fortifying fibre in the claim 48 to 65, wherein select identical polymkeric substance with:
A. with described curable resin modification; And/or
B. apply described fiber; And/or
C. be used to prepare described emulsion.
67. according in the claim 39 to 58 each reinforced composite or according to each fortifying fibre in the claim 40 to 58, wherein said processing is the total surface area that reduces described fortifying fibre.
68. according to the reinforced composite of claim 67 or according to the fortifying fibre of claim 67, the described reduction of wherein said surface-area is to provide by the size that changes described fortifying fibre.
69., wherein change described size by diameter that increases described fortifying fibre and/or the length that reduces described fortifying fibre according to the reinforced composite of claim 68 or according to the fortifying fibre of claim 68.
70. according to the reinforced composite of claim 69 or according to the fortifying fibre of claim 69, the diameter of wherein said fiber is between about 15 to 24 microns.
71. according in the claim 39 to 70 each reinforced composite or according to each fortifying fibre in the claim 40 to 70, the modulus in flexure of wherein said cured composite material is greater than about 3.5GPa.
72. according in the claim 39 to 71 each reinforced composite or according to each fortifying fibre in the claim 40 to 71, the flexural stress of wherein said cured composite material is greater than about 120MPa.
73. according in the claim 39 to 72 each reinforced composite or according to each fortifying fibre in the claim 40 to 72, the elongation at break of wherein said cured composite material is greater than about 2%.
74. according in the claim 39 to 73 each reinforced composite or according to each fortifying fibre in the claim 40 to 73, wherein when when not comparing according to the fiber of handling according to the present invention, described processing is reduced in the catalysis of the resin polymerization in the intermediate phase.
75. according in the claim 39 to 74 each reinforced composite or according to each fortifying fibre in the claim 40 to 74, wherein when when not comparing according to the fiber of handling according to the present invention, described processing reduces the embrittlement of described intermediate phase.
76. according in the claim 39 to 75 each reinforced composite or according to each fortifying fibre in the claim 40 to 75, wherein will add in the described resin at the fiber of the processing between about 5 to 50%w/w.
77. according in the claim 39 to 76 each reinforced composite or according to each fortifying fibre in the claim 40 to 76, wherein described fiber fully is coupled on the described resin to strengthen described resin.
78. method that is used for reducing the embrittlement of matrix material, described matrix material has curable resin and Duo Gen and is scattered in wherein fortifying fibre, the cured resin of contiguous described fortifying fibre limits intermediate phase, described method comprises the following steps: to reduce the total surface area of described fortifying fibre, thereby the corresponding reduction of the described amount of described intermediate phase is provided.
79. according to the method for claim 78, the described reduction of wherein said surface-area is to provide by the size that changes described fortifying fibre.
80., wherein change described size by diameter that increases described fortifying fibre and/or the length that reduces described fortifying fibre according to the method for claim 79.
81. 0 method according to Claim 8, the diameter of wherein said fiber is between about 15 to 24 microns.
82. according to each method in the claim 78 to 81, the total surface area of the described fortifying fibre of wherein said reduction is reduced in total catalytic amount of the resin polymerization in the intermediate phase, thereby reduces the embrittlement of described intermediate phase relatively.
83. a method that is used for molded composites, described method comprise the following steps: to provide the mixture of at least a curable resin and Duo Gen fortifying fibre, described fortifying fibre is according to each described method preparation among the claim 2-38; Described mixture is applied in the mould; And described at least a curable resin is solidified.
84. one kind is passed through the matrix material of the molding of 3 described methods preparations according to Claim 8.
85. liquid curing matrix material, it comprises at least a curable resin and Duo Gen fortifying fibre, make in use, the cured resin of contiguous described fortifying fibre limits intermediate phase, and the processed performance of described intermediate phase that makes of wherein said fortifying fibre is substantially equal to the performance of main body cured resin.
86. liquid curing matrix material, it comprises at least a curable resin and Duo Gen fortifying fibre, be coated with one or more of polymeric coating, hydrophilic surface coating or free radical inhibitors coating on the described fortifying fibre, make when solidifying, the cured resin of contiguous described fortifying fibre limits intermediate phase, and described intermediate phase has the performance that equates basically with the performance of main body cured resin.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210145866.2A CN102731803B (en) | 2005-10-17 | 2006-10-17 | Reinforced composite |
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2005905733A AU2005905733A0 (en) | 2005-10-17 | A Method for Manufacturing Very Short Fibre Polymerisable Liquid Composites | |
| AU2005905733 | 2005-10-17 | ||
| AU2005906723 | 2005-12-01 | ||
| AU2005906723A AU2005906723A0 (en) | 2005-12-01 | A Method for Manufacturing Very Short Fibre Polymerisable Liquid Composites | |
| AU2006900511A AU2006900511A0 (en) | 2006-02-03 | A Method for Manufacturing Very Short Fibre Polymerisable Liquid Composites | |
| AU2006900511 | 2006-02-03 | ||
| AU2006902791A AU2006902791A0 (en) | 2006-05-24 | A New Method for Manufacturing Very Short Fibre Polymerisable Liquid Composites | |
| AU2006902791 | 2006-05-24 | ||
| PCT/AU2006/001536 WO2007045025A1 (en) | 2005-10-17 | 2006-10-17 | Reinforced composite material |
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| CN201210145866.2A Division CN102731803B (en) | 2005-10-17 | 2006-10-17 | Reinforced composite |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103360778A (en) * | 2012-04-10 | 2013-10-23 | 马格-伊索福株式会社 | Composite molding material, and surface-treated glass wool |
| CN104039882A (en) * | 2011-07-06 | 2014-09-10 | 米尔泰奇有限公司 | Resins, resin/fibre composites, methods of use and methods of preparation |
| CN104072961A (en) * | 2014-06-18 | 2014-10-01 | 安徽宁国市高新管业有限公司 | Heat and corrosion resistant glass fiber reinforced plastics composite material |
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| CN115216966A (en) * | 2022-08-09 | 2022-10-21 | 吴怀中 | Fiber bundle, preparation method and application thereof, and fiber-reinforced composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4038243A (en) * | 1975-08-20 | 1977-07-26 | Ppg Industries, Inc. | Glass fiber sizing compositions for the reinforcement of resin matrices |
| US6593255B1 (en) * | 1998-03-03 | 2003-07-15 | Ppg Industries Ohio, Inc. | Impregnated glass fiber strands and products including the same |
| CA2429226C (en) * | 2000-11-17 | 2011-06-07 | Peter Clifford Hodgson | Coupling of reinforcing fibres to resins in curable composites |
| US20040052997A1 (en) * | 2002-09-17 | 2004-03-18 | Ietsugu Santo | Composite pressure container or tubular body and composite intermediate |
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- 2006-10-17 CN CN2006800475540A patent/CN101331176B/en not_active Expired - Fee Related
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| CN104039882B (en) * | 2011-07-06 | 2016-08-24 | 米尔泰奇有限公司 | Resin, resin/fiber composite, its using method and preparation method |
| CN106084706A (en) * | 2011-07-06 | 2016-11-09 | 米尔泰奇有限公司 | Resin, resin/fiber composite, its using method and preparation method |
| CN106189149A (en) * | 2011-07-06 | 2016-12-07 | 米尔泰奇有限公司 | Resin, resin/fiber composite, its using method and preparation method |
| CN106084706B (en) * | 2011-07-06 | 2019-06-14 | 米尔泰奇有限公司 | Resin, resin/fiber composite material, its application method and preparation method |
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| CN103360778A (en) * | 2012-04-10 | 2013-10-23 | 马格-伊索福株式会社 | Composite molding material, and surface-treated glass wool |
| CN103360778B (en) * | 2012-04-10 | 2016-06-15 | 藤田钲则 | It is compounded to form material and surface treated staple glass fibre |
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| CN109715580A (en) * | 2016-09-09 | 2019-05-03 | 普睿司曼股份公司 | Optical fiber coated with polyester coatings |
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| CN115216966A (en) * | 2022-08-09 | 2022-10-21 | 吴怀中 | Fiber bundle, preparation method and application thereof, and fiber-reinforced composite material |
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| ZA200804196B (en) | 2009-04-29 |
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