CA1325496C - Process and compositions for reinforcing structural members - Google Patents
Process and compositions for reinforcing structural membersInfo
- Publication number
- CA1325496C CA1325496C CA000592960A CA592960A CA1325496C CA 1325496 C CA1325496 C CA 1325496C CA 000592960 A CA000592960 A CA 000592960A CA 592960 A CA592960 A CA 592960A CA 1325496 C CA1325496 C CA 1325496C
- Authority
- CA
- Canada
- Prior art keywords
- composition
- structural member
- reinforcing
- kit
- dough
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
- B62D—MOTOR VEHICLES; TRAILERS
- B62D29/00—Superstructures, understructures, or sub-units thereof, characterised by the material thereof
- B62D29/001—Superstructures, understructures, or sub-units thereof, characterised by the material thereof characterised by combining metal and synthetic material
- B62D29/002—Superstructures, understructures, or sub-units thereof, characterised by the material thereof characterised by combining metal and synthetic material a foamable synthetic material or metal being added in situ
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
- B62D—MOTOR VEHICLES; TRAILERS
- B62D21/00—Understructures, i.e. chassis frame on which a vehicle body may be mounted
- B62D21/09—Means for mounting load bearing surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
- B62D—MOTOR VEHICLES; TRAILERS
- B62D21/00—Understructures, i.e. chassis frame on which a vehicle body may be mounted
- B62D21/15—Understructures, i.e. chassis frame on which a vehicle body may be mounted having impact absorbing means, e.g. a frame designed to permanently or temporarily change shape or dimension upon impact with another body
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
Abstract
ABSTRACT OF THE DISCLOSURE
A two-part system for reinforcing a hollow structural member and its method of use are provided. Part A of the two-part system is formed by adding a filler and unexpanded, thermally-expandable microspheres to a liquid thermosetting resin, such as an epoxy resin, in a quantity sufficient to produce a dough-like mass which can be readily kneaded. Part B is formed by adding a filler and a colorant, such as carbon black, to a liquid curing agent, again forming a dough-like mass. The curing agent is compatible with the thermosetting resin to promote cross-linking of the thermosetting resin upon contact with the curing agent.
A hollow structural member is cleared of debris or the like and may be preheated to enhance the rate at which the thermosetting resin cross-links. The two parts are blended together until a reactive third dough of substantially uniform mixture is formed. The uniformity of the blending is confirmed when the reactive third dough attains a uniform color intermediate the color between the colors of part A and part B.
The blended reactive dough is then packed into the cavity of the cleaned structural member. The cavity is then preferably closed with a closure plate. As the curing agent promotes the cross-linking reaction of the thermosetting resin, the exothermic reaction generates heat which is transferred to the unexpanded, thermally-expandable microspheres, causing the microspheres to expand. The expansion of the microspheres causes the reactive dough to rise, substantially filling the cavity. As the reactive dough cures, it bonds rigidly to the surfaces which it contacts. The reactive dough is allowed to fully cure, whereupon a solid lightweight reinforcement member rigidly bonded to the structural member is formed. The reinforced structure has good strength and energy absorption characteristics. The present system is particularly suitable for use in reinforcing motor vehicle structures which have been cold-worked during repair of collision damage.
A two-part system for reinforcing a hollow structural member and its method of use are provided. Part A of the two-part system is formed by adding a filler and unexpanded, thermally-expandable microspheres to a liquid thermosetting resin, such as an epoxy resin, in a quantity sufficient to produce a dough-like mass which can be readily kneaded. Part B is formed by adding a filler and a colorant, such as carbon black, to a liquid curing agent, again forming a dough-like mass. The curing agent is compatible with the thermosetting resin to promote cross-linking of the thermosetting resin upon contact with the curing agent.
A hollow structural member is cleared of debris or the like and may be preheated to enhance the rate at which the thermosetting resin cross-links. The two parts are blended together until a reactive third dough of substantially uniform mixture is formed. The uniformity of the blending is confirmed when the reactive third dough attains a uniform color intermediate the color between the colors of part A and part B.
The blended reactive dough is then packed into the cavity of the cleaned structural member. The cavity is then preferably closed with a closure plate. As the curing agent promotes the cross-linking reaction of the thermosetting resin, the exothermic reaction generates heat which is transferred to the unexpanded, thermally-expandable microspheres, causing the microspheres to expand. The expansion of the microspheres causes the reactive dough to rise, substantially filling the cavity. As the reactive dough cures, it bonds rigidly to the surfaces which it contacts. The reactive dough is allowed to fully cure, whereupon a solid lightweight reinforcement member rigidly bonded to the structural member is formed. The reinforced structure has good strength and energy absorption characteristics. The present system is particularly suitable for use in reinforcing motor vehicle structures which have been cold-worked during repair of collision damage.
Description
1992.021 I 3~5496 PROCESS AND COMPOSITIONS FOR REINFORCING STRUCTURAL MEMBERS
FIELD OF THE INVENTION
The present invention relates generally to processes and compositions for rcinforcing hollow structural members and more specifically deals with a two-part, resin-based system for reinforcing hollow structural members.
BACKGROUN~ OF THE INVENTION
Motor vehicle collisions are a common occurrence in today's highly mobile society. Motor vehicle designers and manufacturers go to great lengths to protect the vehicle occupants from injury by providing vehicle structures having good strength and energy absorption characteristics. It is also a goal of designers to fabric:lte motor vehicle structures which can withstand low-speed impacts without requiring substantial repairs. Although motor vehicle designers and manufacturers have i:
j succeeded in providing high-strength, energy-absorbing structural components, the restoration of these desirable attributes to a motor vehicle which has been damaged in a collision is of considerable concern to after-market vehicle repair facilities.
Particularly in the case of metal structural components, the deformation of a structural member during a collision produces a number of unwanted cffects in terms of both the relative geometry or shape of the part and with respect to the strcngth of the metal. It is a goal of the repair facility to restore to the extent possiblc the original shape of the damaged part so that it can once again carry out its function in the vehicle. It is a furthcr goal, however, of the repair facility to restore the original strength and encrgy absorption charactcristics to the damaged part. While considerablc attcntion has been paid to the restoration of shape in collision damage repair, resulting in numerous mctal rcpair proccdures and devices such as framc-straightening machincs 1992.021 -- I 325~6 and the like, the viability of reinforcemene techniques in collision repair are less developed. It will be appreciated that the feasibility of reinforcement devices and procedures is detcrmined by a number of factors that go beyond merely restoring strength to the d~maged part.
When a metal part is plastically deformed, the internal structure of the metal is changed. Thus, this type of deformation changcs the propcrties of the metal.
The original deformation of the metal structure during a collision as well as its restoration by metal repair straightening opera~ions can be considered work-hardening.
Work-hardening processes may cause brittleness of the work section due to strain-hardening and generally change the strength and energy absorption properties of the part. In many instances, for example, where frame damage has occurrcd resulting in a crumpled, bent or collapsed frame member, a new section of frame rail must be spliced into place. The new rail piece is commonly welded in place using arc or mig welding techniques. In order to reinforce the weld joints or to compensate for the altered compositional characteristics of a section of metal produced by cold-working, a metal plate is typically welded into the rail over the joint or worked region. This has been the traditional approach to reinforcing metal structures, and it has numerous drawbacks.
;~
; A metal plate must be cut to conform to the shape of the part to be repaired. It will be appreciated by those skilled in the art that in many motor vehicles, the vehicle frame comprises a pair of U-shaped pressings or stampings which are welded together by rne~ns of a horizontal longitudinal joint or seam and that each U-shaped :~ pressing defines a channel. Although metal reinforcement plates are at times welded directly to the outside of the hollow rail beam, more often the spot welds connecting the . two U-shaped pressings are bored out, and the more damaged stamping is removed to be rcplaced with a new piece. Having access to the rail channel, the reinforcement plate is usually welded to the rail within this channcl. Hence, the platc must be preciscly cut to fit within this designated are~. Once the plate has been preparcd, it must thcn bc welded in pl3ce. Therc is no assurance that sufficicnt spot welds will be madc to providc a good bond bctween the reinforcement plate and the rail. Morcovcr, the ,: wclding procedurc is time-consuming and requircs the addition;ll skill of arc or mig : 2 , ., j., .
', ",.~
,.:, . .
1992.021 - 1 3254q6 welding on thc part of the repair person. As will be appreciated by those skilled in the art, the welds promote corrosion of the metal parts and thus lead to a reduction in the integ}ity and life of thc repaired members. A closure plate is then typically welded to the flanges of the stnmping for further reinforcement which, with the channel, forms a closed space or csvity in which the metal reinforcement plate is housed.
In addition to these drawbacks, this prior art technique may chnnge the dynamic performance of the reinforced structure during a subsequent collision.
While, as stated, one goal of the repair procedure is to restore the strengthen and energy absorption characteristics of the structural member, the insertion of a metal plate in the rail may in fact reduce the energy absorption of the member or change the frame failure mode. This may result in the exertion of forces on vehicle components which were not designed to withstand these forces. Moreover, the repair procedure may not restore the original strcngth characteristics of the reinforced part. These factors may lend to catastrophic consequences during a subsequent collision.
In order to provide a method and device which compensates for these deficiencies of prior art repair methods, the environment in which these repairs are made rnust be carefully considered. While metal repair should be performed by skilled metal workers, it is often the case that many repair tasks are delegated to poorly trained personnel in neighborhood "bump shops." A lack of care in implementing any repair procedure cnn undermine the efficacy of the repair. Thus, a practical repair procedure must be simple to carry out and should reduce the discretion that is exercised by the repair person. Therefore, it is an object of the present invention to provide n system for 'j reinforcing a structural member which is both simple and reliable.
It is a further object of the present invention to provide a kit for performing rcpairs to structural members which is both economical and which requires minimal prcparation for use. It i5 3, further object thnt such a system rcstore to the cxtcnt possiblc the originnl strength and energy absorption characteristics to a damagcd structural mcmbcr. It is still n further object of the presen~ invention to provide a structural rcinforccmcnt which is both lightw~ight and strong. The present invcntion , - 3 -:;
S ~ .
.~ ' .
-- - ~ 325496 I 992.02 1 provides ~ process and composition which achieves these goals in the form of a two-part, resin-based system which is used to form a reactive dough that expands in place in a hollow structural member to provide a solid, lightweight structural reinforcement.
SUMMARY OF THE INVENl'ION
In accordance with the present invention, there is provided a kit for use in repliring a hollow structural member which includes a first composition having a dough-like consistency and a second dough-like composition. The first composition includes a mixture of a thermosetting resin and unexpanded microspheres. A filler ` material is also preferably included in the first composition in a quantity sufficient to ;. yield the aforementioned dough-like consistency. The second cornposition includes a ;I curing agent which is effective to cross-link and cure the thermosetting resin prcsent in thc first composition. Thc second composition also preferably contains a fillcr to 11 impart the dough-like consistency and further preferably contains a quantity of a colorant sufficient to impart a uniform color to the second composition. This uniform color is preferably substantially different than the color of the first composition. The first and second compositions are preferably contained in separate chambers of a ~1 ~ container where they remain relatively stable until they are mixed and used to reinforce a structural member.
~j `:,3: ~ By combining the first compositlon with the second composition, a third composition is formed which is chemically reactive by virtue of the effect of the curing agent in promoting the cross-llnking or or curing of the thermosetting resin. The , ~ cross-linking of the thermosetting resin which is promoted by the curing agent is :ln exothermic reaction. and the heat of reaction which is evolved raises the temperature of the third composition which in turn further catalyzes the cross-linking reaction and : ~
~ causes thc unexpanded microspheres to expand. Since the third composition is in a "~
dough-like state when it is first formed by the blending together of the first and sccond composi~ions, expansion of the microspheres causes the dough to "risc," thercby increasing the volume of the third composition. As the cross-linking reslction continucs, the thcrmosetting resin forms ~ cured, solid matrix in which the now-expandcd i -4-.
. ~ .
1 992.02 1 microspheres and the filler are embedded, resulting in a rigid, lightweight reinforcement membcr. The provision of a colorant facilitates the blending of the first and second compositions together in th:~t blending is complete when a uniform color is attained intermcdiate between the hues of the first and second compositions.
~1 In another aspect, the present invention provides a process or method for reinforcing a hollow structural member which includes the steps of preparing the aforementioned first composition and preparing the aforementioned second composition which are then blended to form the reactive dough of the third composition. The reactive or, more properly, "reacting" dough is packed into the cavity of a hollow structural membcr being reinforced. The two piece metal assembly is then welded togethcr capturing the dough. The generation of heat during the polymerization of the thermosetting resin causes expansion of the unexpanded microsphercs with concomitant `I
:, increase in the volume of the dough. The expansion of the dough serves to further fill the cavity. As the thermosetting resin cures, it bonds to the surfaces of the structural member forming a uniform, rigid attachmerlt. When the third composition has been , transformed from its initial dough-like consistency to a fully-cured, hardened ¦ ~ reinforcement member, it provides excellent strength and energy absorption characteristics to the structural member which it reinforces. In a preferred embodiment, the hollow structural member which is reinforced is one which has been ¦ damaged in a collision or the like.
. 1 In one embodiment, the thermosetting resin of the present invention is an epoxy resin to which unexpanded, thermaliy-expandable microspheres and a filler are '~ added until a dough-like consistency is achieved. Similarly, a filler is added to a curing 3, agent cap~ble of promoting the cross-linking of an epoxy resin a}oDg with c~rbon black to produce a black dough-like composition. In this embodiment, the two doughs arc blended together just prior to the reinforcement procedure to produce a reactive third dough which is gray in color. Where the present invention is used to reinforcc ~
damaged rail membcr of a motor vehicle, the reactive gray dough is packcd into thc ~, channel of the rail mcmber, and a closure plate is preferably then weldcd in placc across thc channel. As thc rcactivc gr~y dough expands as a result of the hcat gcncrtltcd, ~ -5 -;' f ... .
1992.021 ~ 1 32~4q6 which expands the thermally-expandable m~crosp eres, the dough conforms to the shnpe of the cnvity, contacting and bonding to the adjacent structures. Upon curing, a rigid, lightwcight reinforcement is formed which is securely bonded in place.
The present invention will now be more fully explained in the following dcscription of the preferred embodiments by which those skilled in the art will appreciate the method of making and using the present invention.
These and other meritorious advantages and fentures of the present - invention will be more fully understood with reference to the following description of the preferred embodiments of the invention and in connection with the drawings in which:
BRIEF DESCRIPTION OF THE DRAWINGS
Figure I is a perspective view of a portion of an autornobile in which the front section of a frame side rail is exposed.
v Figure 2 is a U-shaped stamping of a side rail showing ehe composition of the present invention in place in the rail channel with a cover plate shown in exploded view.
.
Figure 3 is a cross-section along lines 3-3 of Figure 2 with the closurc plate in place.
Figure 4 is a flowchart illustrating the steps of the prescnt invention.
( Figure S is a cross-sectional elevationnl view Or the kit of the present invcntion showing side A and side B of the rcinforcemcnt composition housed in sepnrnte cnvitics.
-- 1 3254q~
1 992.02 1 DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to Figure I of the dra~vings, a typical motor vehicle 20 is shown with the front section 22 of frame side rail 24 being exposed. It will bc assumed for the purposes of this discussion that motor vehicle 20 has been involved in a Iow-speed front-end collision and that side rail 24, which is typically formed of steel, sustained damnge, for example, a crumpling or collapse of front section 22 in region 26.
It will also be assumed that front section 22 has now beerl straightened using conventional frame-straightening techniques such as a frame machine. It will also be assumed that frame side rail 24 is constructed of two U-shaped stampings 28 ~nd 30 welded together by means of a horizontal longitudinal joint or seam (not shown). Since region 26 has been plastic~lly deformed during the collision and during the straightening process, its strength and energy absorption characteristics have been dramatically Z altered. It will also be noted that region 26 is a natural bend of frame side rail 24.
Hence, rein~orcement by the conventional method of attaching a metal plate is rendered even more difficult since n metal reinforcing plate would have to conform to the natural bend of region 26. Howcver, the problems inherent in this prior art technique have been avoided by the repair of region 26 using the method and compositions of thepresent invention.
Turning now to Figure 2 of the drawings, an isolated view of region 26 of front section 22 is shown with U-shaped stamping removed and closure plate 32 illustrated as exploded from U-shaped stamping 30. Reinforcement member 34 is seen substantially filling a section of channel 36 and rigidly bonded to the inner surfaccs of U-shaped channel 30. While closure plate 32 is shown removed from its attachment at flanges 38 and 40 of U-shaped member 30, in actuality, closure plate 32 is attached to IJ-shaped stamping 30 by spot welds at flanges 38 and 40 and by the rig;d attachment of reinforcement member 34 to closure plate 32. This relationship is illustrated morc clcarly in Figure 3 which is a cross-section along lines 3-3 of Figure 2. There, closure plate 32 is shown weldcd in place on U-shaped stamping 30 at flangcs 38 and 40. It can be secn that reinforccmcnt member 34 completcly occupies a portion of channel 36 in contact with thc surrounding surfaccs. Reinforcement membcr 34 is in its curcd stntc '', . .
: . ~
,.' ,~ ' . : ~ .
1 992.02 1 such that it is a solid body comprising a cross-linked epoxy resin matrix 42 in which particles of filler 44 and expanded microspheres 46 are shown. It is important to point out that reinforcement member 34 is not shown to scale and that the sizes of thcexpanded microspheres 46 and filler particles 44 are greatly exaggerated for thepurposes of illustration. A more detailed explanation of the compositional characteristics of reinf orcement 34 will f ollow. In this manner, reinf orcement member 34 serves to rcinforce region 26 of frame side rail 24 such that during a subsequent, second collision, region 26 of frame side rail 24 will respond in a fashion closely similar to that of the original part.
Reinforcement member 34 is preferably formed in the following manner which consltitutes the reinforcement repair process of the present invention.
Referring now to Figure 4 of the drawings, the first step of the procedure involves the preparation of the first composition or side A of the invention. Side or part A is prepared by slowly adding a filler and unexpanded, thermally-expandable microspheres to a liquid epoxy resin or prepolymer until a dough-like consistency is attained. The ingredients can be mixed in any convenient container using a conventional mixer, although undue shearing should probably be avoided. As will be more fully appreciated hereinafter, in the most preferred embodiment, side A, and side or part B, are provided pre- mixed in the form of a two-part kit. The mixing or blending together of the ingredients to form side A can be carried out at ambicnt temperature and pressure ~; with no unusual constraints on the process parameters.
i~ The consistency of side A, as stated, is dough-like and can be compared to kneaded bread dough. The consistency of side A should be sufficiently firm, having enough body such that no substantial flow of the material takes place. It should not bc in a true liquid or "runny" state. It should, however, be soft enough so that it can be easily kneaded or blended with side B without undue effort by the repair person. Accordingly, it is to be remembered that one of the significant advantagcs of the present invention is its ease of use.
) ,." ' ~
"~ ' .~ . '';
- 13254q6 1 992.02 1 The concentration or proportion of each ingredient of side A does not appear to be critical and may thus vary somewhat so long as the principles of thc present invention are faithfully observed. The thermosetting resin component thus comprises from about 5% to about 99% by weight of side A, preferably from about 20% to about 90% by weight of side A, and most preferably from about 65% to 85% by weight of side A. Any number of thermosetting resins may be suitable for use in the present invention, although epoxy resins are particularly preferrcd due to their exccllent adhesion characteristics, rapid rate of curing, low-temperature curing characteristics, and the high strengeh exhibited by the fully cured resin. As will be appreciated by those skilled in the art, epoxy resins in the liquid state can be referred to as prepolymers in which the number of repeating units of the polymer is low enough such that the resin flows readily during preparation of side A. A nurmber of epoxy resins may be suitable for use in formulating side A, including epoxy novolak resin, cycloaliphatic epoxide resin, aliphatic epoxy resin, and other similar epoxy resins. Most preferred is bisphenol A-epichlorohydrine resin. A suitable bisphenol A-epichlorohydrine resin is available under the trademark "Epi-Rez 510" from the Interez Corporation.
In addition to the aforementioned attributes, the preferred thermosetting resins of the present invention are both economical, have a low order of shrinkage on cure, produce no cure byproducts, and have chemical and environmental resistance. The chemistry and polymerization reactions or curing mechanisms of the epoxy resins are well understood and thus their preparation will not be detailed.
!~ The unexpanded microspheres used in preparing side A of the present invention are preferably activated or expanded by thermal action. In addition to providing a lightweight reinforcement member due to their low density, the expandablc microsphcres function in the present invention as an expanding agent which, upon activation, C;IUSCS the reactive dough of the prescnt invention to "rise" or expand such that it fills the cavity in which it is d.sposed. By expanding in this manner, the reactivc dough makcs excellent contact with surrounding structures, filling any small voids and conforming to irregulnr surfaces. Unexpanded microsphcres are ~enerally organic in naturc and m~y be obtaincd from a numbcr of sources. The preferrcd uncxpandcd, :,, : .
` - 1 325496 1 992.02 1 thermally-expandable microspheres have an average diameter of approximately 5 rnicrons to about 7 microns which increases to about 40 microns to about 60 microns upon expansion. The preferred beads are thermally activated by the he~t generated in the exothermic polymerization reaction in which the therrnosetting resin of side or part A
thus should expand at temperatures between about 100 degrees C to about 120 degrees C.
Two particularly preferred types of unexpanded, thermally-expandable polyvinylidcne chloride microspheres are those sold under the trademark "Expancel 551-DU" sold by the Expancel Corporation. Other equivalent expandable rnicrospheres which sre suitable ' for use in the present invention will be known to those skilled in the art. Unexpanded, thermally-expandable microspheres comprise from about .1% by weight to about 20% by weight, preferably from about .5% by weight to about 10% by weight, and most preferably from about 1% by weight to about 3% by weight of side A of the present nvention.
~,j In order to add bulk to the first composition, to extend the thermosetting resin, and to give the first composition its dough-like consistency, a filler is added along with the unexpanded, thermally-expanded microspheres. It is to be understood that the exac~ order in which the three components of part A are blended :, together is not critical, although it is preferred that the dry constituents, that is, the ~3 filler and unexpanded, thermally-expandable microspheres, be added slowly to the epoxy `J resin. Also, if the ranges set forth for the three constituents in a given case do not .1 `~ provide the op~imum dough-like consistency, the viscosity of the dough is most easily adJusted by adjusting the amount of filler which is used.
A number of fillers are suitable for use herein, alone or in combination with one another, such as calcium carbonate, talc (hydrated magnesium silicatc), and kaolinite (hydrated aluminum silicate). Various clays may be suitable.
',,~
Othcr fillers which m~y be useful in the present invention include alumina trihydratc, feldspar ~anhydrous alkal; alumina silicate), and silica. Solid glass sphercs could bc uscd, although they are not necessarily beneficial in tcrms of density. Most prefcrrcd ..'~
~i for usc hcrcin ~rc hollow glass spheres, also known as glass bubbles or glass balloons, having an avcrage diamcter less than about 70 microns. Thcse hollow glass .' ::
:, . , ., .
- 1 3254q6 1 992.02 1 microsphcres are preferred due to their low density and high strength. While multicellular hollow microspheres may be suitable, the unicellular type are known to work well. Also, organic hollow microspheres may be a suitable filler. These hollow microsphercs may be used in combination with miner~l fillers to make up the total concentratiort of filler. Filler comprises from about .5% to about 90% by weight, preferably from about 5% to ~bout 60% by weight and most prefcrably from about 20%
to 30% by weight of part A.
Referring again to Figure 4 of the drawings, the next step of the present invention is the preparation of the second composition or part B. Part or side B
includes a curing agent or hardener as the active agent which must be compatible with the thermosetting resin which is used to formulate part A. That is~ the curing agent in part B must be capable of promoting cross-linking of the thermosetting resin which is used in the first composition. This is critical since the final reactive dough which is prepared by blending together part A and part B must undergo cross-linking to cure the thermosetting resin of part A. A number of curing agents will be known to those skilled in the art for this purpose. Both the nature of the curing agent and the concentration of curing agent used should in the final reactive dough promote a cross^linking reaction which is rapid and moderately exothermic to generate the heat necessa~y to expand the unexpanded, thermally-expandable microspheres. However, the rate of cure should not be so rapid that the reactive dough hardens before adequate time is allowed for it to bc hand-packed into a hollow structural member. Therefore~ and although this period may vary widely, it is preferred that the reactive dough which is formed by blendin~ together part A and part B of the presellt invention should remain fairly dough-like for a period of about thirty minutes after blending. This period will be adequate on most occasions.
Substantially full cure should be complete in about twenty-four hours.
Thercfore, a curing a&ent is present in part B at a concentration ot about 10% to about 90% by weight, preferably about 30% to about 85% by wcight, and ~, most prefcrably from about 60% to about 75% by wcight of part B. Where thc thermosctting resin of part A is an epoxy resin as preferrcd, suitable curing agents includc aliphatic amines and aliphatic poly~mincs such as primary polyamincs and I I -., . ~
1992.021 ~ 4 9 6 - ~ second~ry poly~mines, and polyanides. bl'et~yl'enetriamine and tricthyleDeletramine arc particularly prcferred. A particularly preferrcd cllring agent ror use in part B
'I where part A includes an epoxy resin is that sold under the ~rademark "Interez 826 H~rdener" avail~ble î rom the Interez Corporation. "Intercz 826 H~rdcner" is an aliphatic amine adduct partially re~cted with an epo~y re:sin. Aliphatic ~mido amines *
such as "Epicure 856" also available from Intcrez Corporation m~y also be suitJble.
Again, the second composition which is part or side B of the kit has ~
dough-likc consistency similar to the consistealcy of part A. This is achieved by adding to the curing agcnt, prefcrably a liquid or a solution, a quaneity of filler which is sufficicnt to raisç the ~iscosity of part B to a dough-like consistcncy. The same considerations generally applic~ble to selecting a filler for part A are cqually applic~ble for part B and the aforcmentioned list of fillers arc acceptable. Due to their excellcnt durability and density charactcristics, hollow glass microsph¢res arc preferred for use 35 fillcr in part ~. Particularly preferred are those hollow glass microspheres sold under the tradem~rk "3M C15" by the 3M Compa~y. F~llcr comprises from about .5% to about ~0% by weight, prcfcrably from about 109~ to abou~ 7Q% by wei~ht, and most preferably from about 20% to aboul 40% by wcight of part B. As stated~ it is ~hc ~ttainment of the dough-like consistency rather than thc spccific concentration of f;ller which is3 impor~ant in formulating part B.
, As prcviously explained, in ordcr to simplif y the process of determining when pare A and part B have bee~ uniformly mixcd or blendcd together, a color~nt is addcd to cithor part A or part B. 1~ is preferrcd that the coloraDt be added to part B. The addition of the colorant to part B is preferred sincc, as will be shown, p~rt A ~nd part B re proYidcd ;n thc final reac~iYc dough In a volumetric rstio of abou~ four parts to about one part. That is, about four to five parts of p~rt A are addcd to about one p2rt of part B. By providing ~he color~nt in the dough of lesser volume, more 3~ blending will gener~lly bc required ~o re~ch a unirorm color which gives gre3tcr assur~ncc Or uni~orm mixing. Thc color~nts which ~re prcferrcd for use in the prescn~
invcntion c~n bc eithcr dyes or pigments ~nd prefer~bly cornprise inorganic or organic ~, pigmcnt which is c~sily dispersiblc in part B. A number of hues ~re accept3ble, bul is *Trade Mark .', ~,.', .
.
, , - 1 3 ~ 5 4 9 6 1 992.Q2 1 preferred that black be used. Generally, the constituents of part A when mixed will provide a white dough. Thus, by coloring part B black, uniform blending is achieved when the reactive dough is uniformly gray. Thus, dyes such as nigrosines, for example, solvent black 5 or solvent black 7 may be used, and most preferably carbon black is used as the colorant in part B. Preferred are thermal and furnnce blacks which are outstanding colorants and which also protect the final reinforcement structure from ultraviolet degradation. The quantity of colorant which is used is that amoùnt sufficient to uniformly color part B. Typically, from about 0.05~b to about 10% by weight, preferably from about .1% to about 3% by weight and most preferably from-. about .5% to about 1.0% by weight of part B is added to part ~ as the colorant.
, The mixing sequence for part B is not critical, although it will usually include the slow addition of filler and carbon black to a liquid curing agent which is stirred and then kneaded to its dough-like consistency.
,~
A number of other ingredients can be used to further enhance the ~' properties of the present invention. For example, a coupiing agent can be added to part ;' A to modify the interface of the thermosetting resin matrix and an inorganic filler such . that a more solid structure is attained. A coupling agent where utilized would typically ~, be included in part B, that is, the second composition. Suitable coupling agents include silanes such as gama-chloropropyl-trimethoxysilane or tritanates such as isopropyl-tri(dioctylpyrophosphate)titanate. Certain accelerators may be useful in ~art B to , increase the activity of the curing agent in promoting cross-linking of the thermosetting resin.
.
.1 Other additives such as anti-oxidants or fibrous reinforcement matcrials may be useful. Suitable fibrous reinforcements may include chopped aramid fibers, choppcd carbon fibers, chopped glass strnins and millcd glass fibers. The concentrations of thcse materials may vaiy so long as the desircd durability of thc final ;~ reinforccment membcr, workability of the reactive dough and the othcr objects of the ~ present invention arc achicvcd.
., ~
1 992.02 1 Referring now to Figures 2 and 4 of the drawings, region or section 26 is prepared for reinforcement by the present inverltion in the following manner. First, cavity or channel 36 is exposed such that reinforcement member 34 can be formed in place. Thus, the next step of the present invention is the preparation of the hollow structural membcr to receive the reactive dough. As stated, although the present invention is suitable for use in reinforcing plastic structural members, it is anticipated that the primary application of the present invention will be for use in reinforcing metal hollow structural members which have been damaged, such as in a collision. The surfaces of U-shaped stamping 30, which will be in contact with reinforcement member 34, are cleaned for good contact and adhesion by the reactive dough. This cleaning process may include blowing off excess dirt and dust and preferably includes a brief wash with acetone or alcohol. Preferably, rust and any weld scale present should be removed. Once the surface of U-shaped stamping 30 has been prepared, the reactivc dough will be used to form reinforcement member 34 as prepared.
As stated, it is contemplated that the present invention will be made available as a kit and, referring now to Figure 5 of the drawings, kit 4$ is shown comprising container 50 having receptacles or cavities 52 and 54. Receptacles 50 and 54 are separated by partition 56. Container 50 is constructed of a material which is substantially non-reactive with respect to its contents. Receptacle 54 houses the first compos;t}on or part A 58 which is the thermosetting resin dough composition.
Receptacle 52 contains part B 60 which is the curing agent dough composition.
Substantially air-tight lid 62 is also provided.
In order to prepare the reactive dough, part A 58 and part B 60 are ~Icnded together uniformly. For the preferred compositions of part A 58 and part B 60, the two parts are blended together in the approximate ratio of bctween about four parts part A to about one part part B in parts by volume and five parts A to about one part B in parts by volume. That is, the volume of part A 58 which is blcnded with part B 60 is approximately four times greater than the volume of part B 60. Since part B 60 includes a colorant, preferably carbon black, uniformity of blending of ptlrt A and part B can be obscrvcd once the combincd or blended reactive dough has a uniform gr~y color. It !
,' , .
~"' ' , ' .
,'' ' ' , .
~ - 1 32549~
1 992.02 1 should bc pointed out that it may be desirable to add a pigment to part A such as titanium oxidc if the ingredients of part A yield a dough which is not white. Once part A and part B are blended together to form the reactive dough, a number of physical and chcmical changes occur. As the curing agent contacts the thermosetting resin, the polymerization or cross-linking of the thermosetting resin is promoted in the process of curing the thermosetting resin. As the thermosetting resin cures, the reactive dough will bccome even more viscous. The une~cpanded, ther nally-expandable microspheres, which are now uniformly distributed throughout the reactive dough, will begin toexpand in response to the heat generated during the exothermic cross-linking reaction.
! This expansion of the expandable microspheres causes the reactive dough to rise or expand. Thus, the next step of the invention is the packing of the reactive dough into i` cavity 36 in contact with U-shaped stamping 30 in region 26 to be reinforced.
Both the blending of part A and part B to form the reactis~e dough and the packing of the reactive dough into channel 36 are preferably performed by hand, although it may be possible to automate this procedure. When hand-blending and hand--~ packing, the repair person should use solvent- resistant gloves or the like so that direct contact between the reactive dough aDd the repair person's hands is not made. As `1 stated, the preferred compositions of the present invention produce a reactive dough which can be easily worked by hand for approximately thirty minutes, during which time the reactive dough continually rises or expands. The reactive dough should be packed into cavity 36 such that the area or region 26 to be reinforced is substantially .~ filled. Once the reactive dough has been packed into cavity 36, it is preferred that closure plate 32 be welded onto U-shaped stamping 30 such that the reactive dough is enclosed in cavity or channel 36. This may be accomplished most readi}y by spot welding closure plate 32 at flanges 38 and 40. It may be desirable to increase the rate of curing and expansion of the reactive dough by heating region 26 of U-shaped member 30 1~' Wittl a heat gun or thc likc prior to packing the reactive dough into channcl 36. Thc heat encrgy will not only incrcase the rate of the cross-linking reaction of thc thcrmosctting rcsin, but also will increasc the rate at which the thcrmally- cxpandablc microsphcrcs expnnd. Also, the heat gencrated during the welding, such as mig welding, of ctosurc plntc 32 on U-shaped stamping 30 ~t region 26 gener;llly also hcats thc reactive ~ ~ .
- 1 325~96 1 992.02 1 dough, enhancing its cure rate. As the reactive dough expands, it fills any small cracks, voids, or surface irregularities in region 26 of U-shaped stamping 30 and bonds by adhesion to U-shaped stamping 30 and closure plate 32. In approximately twenty-four hours, the reactive dough has substantially fully cross-linked and the thermally-expandable microspheres have substantially fully expanded such that reinforcement member 34 shown in Figure 2 is formed. Thus, thc last step of the invention is the attachment of closure plate 32 after wllich the reactive dough cures to form reinforcement member 34.
Reinforcement member 34 has good strength and energy absorption characteristics and in most instances will restore the original characteristics of the damagcd part which has been repaired and reinforced by the present invention. Due to the compositional characteristics of reinforcement member 34, and due to its expansion in channel 36, acoustical dampening is achieved which eliminates any rattle or the like by cover plate 32. A mating section of U-shaped stamping 28 may then be welded onto cover plate 32 if desired. Reinforcement member 3~ also provides good corrosion resistance which is a significant problem in prior art metal plate reinforcing techniques.
In addition, a heat lamp or the like may be emplo~ed to facilitate the cure of the reactive dough and expansion of the microspheres, if desired.
The present invention may be used to reinforce hollow sections other than vehicle frames or the like~ including boat hulls or other structures where a Iightweight, strong reinforcement is desired or in automotlve roof structures such as the ;~pillars. Kit 48 is both convenient and easy to implement and requires no comple:c ~imixing of hazardous materials nor does it require exact measurements or temperature rnnges to be observed.
, - 1 6--1 992.02 1 While a particular embodiment of this invention is shown and described herein, it will be understood, of course, that the inYention is not to be limited thereto since many modifications may be made, particularly by those skilled in the art, in light of this disclosure. It is contemplated therefore by the appended claims to cover any such modifications as fall within the true spirit and scope of this invention.
The following example further illustrates the method of making and using the present invention and is not intended to in any way limit the scope of this invention i EXAMPLE
A two-part system was prepared in accordance with the procedures and parameters set forth in the foregoing description of the preferred embodiments as 3 follows. ''3MC15" microspheres and "Expancel 551-DU" were added slowly to "Interez 510" epoxy, and the composition was stirred and then kneaded to a dough-like consistency. This was carried out at ambient temperature and pressure to yield adough-like composition or part A having the following compositional make-up:
~L~
;l Interez 510 Epoxy 73.0 parts by weight 3 3M C15 Microspheres 25.5 parts by weight Expancel S5 1 -DU 1.5 parts by weigh~
Part A was then placed in a closed container for later use.
'1 Part B was prepared, again at ambient temperature and pressure, by slowly adding 3M C15 microspheres and carbon black to "Interez 826" hardener. The ingredients wcrc mixcd and then kneaded to a dough-like consistency. P~rt B had tllc following compositional make-up:
. .
fl, ,~,, ., . . .
; :
I 992.02 1 Part B
Interez 826 Hardener 69.4 parts by weight 3M C 15 Microspheres 30.0 parts by weight Carbon Black 0.6 parts by weight The dough-like part B was then placed in a closed container for subsequent use.
.
, Four parts by volume of part A were then blended by kneading with one part by volume of part B until the reactive dough so formed had a uniform gray :
appearance. The kneading process took only a few minutes, and the reactive dough was then packed into a C-section to be reinforced. The channel of the C-section was then closed with a closure plate, and the dough was allowed to rise in place. In approximately twenty-four hours, the reactive dough had fully cured to form a reinforcement member. The reinforced (:-section exhibited good strength ~ .
i~ characteristics.
,, .
' ,, .
., .~
~ ., `I;
,.
.~ .
. 1 '.~
, . ~
. ...
~il ri , .
,. ..
;
i~
: ~' - 1 8-;
.:
., -, ,, :
FIELD OF THE INVENTION
The present invention relates generally to processes and compositions for rcinforcing hollow structural members and more specifically deals with a two-part, resin-based system for reinforcing hollow structural members.
BACKGROUN~ OF THE INVENTION
Motor vehicle collisions are a common occurrence in today's highly mobile society. Motor vehicle designers and manufacturers go to great lengths to protect the vehicle occupants from injury by providing vehicle structures having good strength and energy absorption characteristics. It is also a goal of designers to fabric:lte motor vehicle structures which can withstand low-speed impacts without requiring substantial repairs. Although motor vehicle designers and manufacturers have i:
j succeeded in providing high-strength, energy-absorbing structural components, the restoration of these desirable attributes to a motor vehicle which has been damaged in a collision is of considerable concern to after-market vehicle repair facilities.
Particularly in the case of metal structural components, the deformation of a structural member during a collision produces a number of unwanted cffects in terms of both the relative geometry or shape of the part and with respect to the strcngth of the metal. It is a goal of the repair facility to restore to the extent possiblc the original shape of the damaged part so that it can once again carry out its function in the vehicle. It is a furthcr goal, however, of the repair facility to restore the original strength and encrgy absorption charactcristics to the damaged part. While considerablc attcntion has been paid to the restoration of shape in collision damage repair, resulting in numerous mctal rcpair proccdures and devices such as framc-straightening machincs 1992.021 -- I 325~6 and the like, the viability of reinforcemene techniques in collision repair are less developed. It will be appreciated that the feasibility of reinforcement devices and procedures is detcrmined by a number of factors that go beyond merely restoring strength to the d~maged part.
When a metal part is plastically deformed, the internal structure of the metal is changed. Thus, this type of deformation changcs the propcrties of the metal.
The original deformation of the metal structure during a collision as well as its restoration by metal repair straightening opera~ions can be considered work-hardening.
Work-hardening processes may cause brittleness of the work section due to strain-hardening and generally change the strength and energy absorption properties of the part. In many instances, for example, where frame damage has occurrcd resulting in a crumpled, bent or collapsed frame member, a new section of frame rail must be spliced into place. The new rail piece is commonly welded in place using arc or mig welding techniques. In order to reinforce the weld joints or to compensate for the altered compositional characteristics of a section of metal produced by cold-working, a metal plate is typically welded into the rail over the joint or worked region. This has been the traditional approach to reinforcing metal structures, and it has numerous drawbacks.
;~
; A metal plate must be cut to conform to the shape of the part to be repaired. It will be appreciated by those skilled in the art that in many motor vehicles, the vehicle frame comprises a pair of U-shaped pressings or stampings which are welded together by rne~ns of a horizontal longitudinal joint or seam and that each U-shaped :~ pressing defines a channel. Although metal reinforcement plates are at times welded directly to the outside of the hollow rail beam, more often the spot welds connecting the . two U-shaped pressings are bored out, and the more damaged stamping is removed to be rcplaced with a new piece. Having access to the rail channel, the reinforcement plate is usually welded to the rail within this channcl. Hence, the platc must be preciscly cut to fit within this designated are~. Once the plate has been preparcd, it must thcn bc welded in pl3ce. Therc is no assurance that sufficicnt spot welds will be madc to providc a good bond bctween the reinforcement plate and the rail. Morcovcr, the ,: wclding procedurc is time-consuming and requircs the addition;ll skill of arc or mig : 2 , ., j., .
', ",.~
,.:, . .
1992.021 - 1 3254q6 welding on thc part of the repair person. As will be appreciated by those skilled in the art, the welds promote corrosion of the metal parts and thus lead to a reduction in the integ}ity and life of thc repaired members. A closure plate is then typically welded to the flanges of the stnmping for further reinforcement which, with the channel, forms a closed space or csvity in which the metal reinforcement plate is housed.
In addition to these drawbacks, this prior art technique may chnnge the dynamic performance of the reinforced structure during a subsequent collision.
While, as stated, one goal of the repair procedure is to restore the strengthen and energy absorption characteristics of the structural member, the insertion of a metal plate in the rail may in fact reduce the energy absorption of the member or change the frame failure mode. This may result in the exertion of forces on vehicle components which were not designed to withstand these forces. Moreover, the repair procedure may not restore the original strcngth characteristics of the reinforced part. These factors may lend to catastrophic consequences during a subsequent collision.
In order to provide a method and device which compensates for these deficiencies of prior art repair methods, the environment in which these repairs are made rnust be carefully considered. While metal repair should be performed by skilled metal workers, it is often the case that many repair tasks are delegated to poorly trained personnel in neighborhood "bump shops." A lack of care in implementing any repair procedure cnn undermine the efficacy of the repair. Thus, a practical repair procedure must be simple to carry out and should reduce the discretion that is exercised by the repair person. Therefore, it is an object of the present invention to provide n system for 'j reinforcing a structural member which is both simple and reliable.
It is a further object of the present invention to provide a kit for performing rcpairs to structural members which is both economical and which requires minimal prcparation for use. It i5 3, further object thnt such a system rcstore to the cxtcnt possiblc the originnl strength and energy absorption characteristics to a damagcd structural mcmbcr. It is still n further object of the presen~ invention to provide a structural rcinforccmcnt which is both lightw~ight and strong. The present invcntion , - 3 -:;
S ~ .
.~ ' .
-- - ~ 325496 I 992.02 1 provides ~ process and composition which achieves these goals in the form of a two-part, resin-based system which is used to form a reactive dough that expands in place in a hollow structural member to provide a solid, lightweight structural reinforcement.
SUMMARY OF THE INVENl'ION
In accordance with the present invention, there is provided a kit for use in repliring a hollow structural member which includes a first composition having a dough-like consistency and a second dough-like composition. The first composition includes a mixture of a thermosetting resin and unexpanded microspheres. A filler ` material is also preferably included in the first composition in a quantity sufficient to ;. yield the aforementioned dough-like consistency. The second cornposition includes a ;I curing agent which is effective to cross-link and cure the thermosetting resin prcsent in thc first composition. Thc second composition also preferably contains a fillcr to 11 impart the dough-like consistency and further preferably contains a quantity of a colorant sufficient to impart a uniform color to the second composition. This uniform color is preferably substantially different than the color of the first composition. The first and second compositions are preferably contained in separate chambers of a ~1 ~ container where they remain relatively stable until they are mixed and used to reinforce a structural member.
~j `:,3: ~ By combining the first compositlon with the second composition, a third composition is formed which is chemically reactive by virtue of the effect of the curing agent in promoting the cross-llnking or or curing of the thermosetting resin. The , ~ cross-linking of the thermosetting resin which is promoted by the curing agent is :ln exothermic reaction. and the heat of reaction which is evolved raises the temperature of the third composition which in turn further catalyzes the cross-linking reaction and : ~
~ causes thc unexpanded microspheres to expand. Since the third composition is in a "~
dough-like state when it is first formed by the blending together of the first and sccond composi~ions, expansion of the microspheres causes the dough to "risc," thercby increasing the volume of the third composition. As the cross-linking reslction continucs, the thcrmosetting resin forms ~ cured, solid matrix in which the now-expandcd i -4-.
. ~ .
1 992.02 1 microspheres and the filler are embedded, resulting in a rigid, lightweight reinforcement membcr. The provision of a colorant facilitates the blending of the first and second compositions together in th:~t blending is complete when a uniform color is attained intermcdiate between the hues of the first and second compositions.
~1 In another aspect, the present invention provides a process or method for reinforcing a hollow structural member which includes the steps of preparing the aforementioned first composition and preparing the aforementioned second composition which are then blended to form the reactive dough of the third composition. The reactive or, more properly, "reacting" dough is packed into the cavity of a hollow structural membcr being reinforced. The two piece metal assembly is then welded togethcr capturing the dough. The generation of heat during the polymerization of the thermosetting resin causes expansion of the unexpanded microsphercs with concomitant `I
:, increase in the volume of the dough. The expansion of the dough serves to further fill the cavity. As the thermosetting resin cures, it bonds to the surfaces of the structural member forming a uniform, rigid attachmerlt. When the third composition has been , transformed from its initial dough-like consistency to a fully-cured, hardened ¦ ~ reinforcement member, it provides excellent strength and energy absorption characteristics to the structural member which it reinforces. In a preferred embodiment, the hollow structural member which is reinforced is one which has been ¦ damaged in a collision or the like.
. 1 In one embodiment, the thermosetting resin of the present invention is an epoxy resin to which unexpanded, thermaliy-expandable microspheres and a filler are '~ added until a dough-like consistency is achieved. Similarly, a filler is added to a curing 3, agent cap~ble of promoting the cross-linking of an epoxy resin a}oDg with c~rbon black to produce a black dough-like composition. In this embodiment, the two doughs arc blended together just prior to the reinforcement procedure to produce a reactive third dough which is gray in color. Where the present invention is used to reinforcc ~
damaged rail membcr of a motor vehicle, the reactive gray dough is packcd into thc ~, channel of the rail mcmber, and a closure plate is preferably then weldcd in placc across thc channel. As thc rcactivc gr~y dough expands as a result of the hcat gcncrtltcd, ~ -5 -;' f ... .
1992.021 ~ 1 32~4q6 which expands the thermally-expandable m~crosp eres, the dough conforms to the shnpe of the cnvity, contacting and bonding to the adjacent structures. Upon curing, a rigid, lightwcight reinforcement is formed which is securely bonded in place.
The present invention will now be more fully explained in the following dcscription of the preferred embodiments by which those skilled in the art will appreciate the method of making and using the present invention.
These and other meritorious advantages and fentures of the present - invention will be more fully understood with reference to the following description of the preferred embodiments of the invention and in connection with the drawings in which:
BRIEF DESCRIPTION OF THE DRAWINGS
Figure I is a perspective view of a portion of an autornobile in which the front section of a frame side rail is exposed.
v Figure 2 is a U-shaped stamping of a side rail showing ehe composition of the present invention in place in the rail channel with a cover plate shown in exploded view.
.
Figure 3 is a cross-section along lines 3-3 of Figure 2 with the closurc plate in place.
Figure 4 is a flowchart illustrating the steps of the prescnt invention.
( Figure S is a cross-sectional elevationnl view Or the kit of the present invcntion showing side A and side B of the rcinforcemcnt composition housed in sepnrnte cnvitics.
-- 1 3254q~
1 992.02 1 DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to Figure I of the dra~vings, a typical motor vehicle 20 is shown with the front section 22 of frame side rail 24 being exposed. It will bc assumed for the purposes of this discussion that motor vehicle 20 has been involved in a Iow-speed front-end collision and that side rail 24, which is typically formed of steel, sustained damnge, for example, a crumpling or collapse of front section 22 in region 26.
It will also be assumed that front section 22 has now beerl straightened using conventional frame-straightening techniques such as a frame machine. It will also be assumed that frame side rail 24 is constructed of two U-shaped stampings 28 ~nd 30 welded together by means of a horizontal longitudinal joint or seam (not shown). Since region 26 has been plastic~lly deformed during the collision and during the straightening process, its strength and energy absorption characteristics have been dramatically Z altered. It will also be noted that region 26 is a natural bend of frame side rail 24.
Hence, rein~orcement by the conventional method of attaching a metal plate is rendered even more difficult since n metal reinforcing plate would have to conform to the natural bend of region 26. Howcver, the problems inherent in this prior art technique have been avoided by the repair of region 26 using the method and compositions of thepresent invention.
Turning now to Figure 2 of the drawings, an isolated view of region 26 of front section 22 is shown with U-shaped stamping removed and closure plate 32 illustrated as exploded from U-shaped stamping 30. Reinforcement member 34 is seen substantially filling a section of channel 36 and rigidly bonded to the inner surfaccs of U-shaped channel 30. While closure plate 32 is shown removed from its attachment at flanges 38 and 40 of U-shaped member 30, in actuality, closure plate 32 is attached to IJ-shaped stamping 30 by spot welds at flanges 38 and 40 and by the rig;d attachment of reinforcement member 34 to closure plate 32. This relationship is illustrated morc clcarly in Figure 3 which is a cross-section along lines 3-3 of Figure 2. There, closure plate 32 is shown weldcd in place on U-shaped stamping 30 at flangcs 38 and 40. It can be secn that reinforccmcnt member 34 completcly occupies a portion of channel 36 in contact with thc surrounding surfaccs. Reinforcement membcr 34 is in its curcd stntc '', . .
: . ~
,.' ,~ ' . : ~ .
1 992.02 1 such that it is a solid body comprising a cross-linked epoxy resin matrix 42 in which particles of filler 44 and expanded microspheres 46 are shown. It is important to point out that reinforcement member 34 is not shown to scale and that the sizes of thcexpanded microspheres 46 and filler particles 44 are greatly exaggerated for thepurposes of illustration. A more detailed explanation of the compositional characteristics of reinf orcement 34 will f ollow. In this manner, reinf orcement member 34 serves to rcinforce region 26 of frame side rail 24 such that during a subsequent, second collision, region 26 of frame side rail 24 will respond in a fashion closely similar to that of the original part.
Reinforcement member 34 is preferably formed in the following manner which consltitutes the reinforcement repair process of the present invention.
Referring now to Figure 4 of the drawings, the first step of the procedure involves the preparation of the first composition or side A of the invention. Side or part A is prepared by slowly adding a filler and unexpanded, thermally-expandable microspheres to a liquid epoxy resin or prepolymer until a dough-like consistency is attained. The ingredients can be mixed in any convenient container using a conventional mixer, although undue shearing should probably be avoided. As will be more fully appreciated hereinafter, in the most preferred embodiment, side A, and side or part B, are provided pre- mixed in the form of a two-part kit. The mixing or blending together of the ingredients to form side A can be carried out at ambicnt temperature and pressure ~; with no unusual constraints on the process parameters.
i~ The consistency of side A, as stated, is dough-like and can be compared to kneaded bread dough. The consistency of side A should be sufficiently firm, having enough body such that no substantial flow of the material takes place. It should not bc in a true liquid or "runny" state. It should, however, be soft enough so that it can be easily kneaded or blended with side B without undue effort by the repair person. Accordingly, it is to be remembered that one of the significant advantagcs of the present invention is its ease of use.
) ,." ' ~
"~ ' .~ . '';
- 13254q6 1 992.02 1 The concentration or proportion of each ingredient of side A does not appear to be critical and may thus vary somewhat so long as the principles of thc present invention are faithfully observed. The thermosetting resin component thus comprises from about 5% to about 99% by weight of side A, preferably from about 20% to about 90% by weight of side A, and most preferably from about 65% to 85% by weight of side A. Any number of thermosetting resins may be suitable for use in the present invention, although epoxy resins are particularly preferrcd due to their exccllent adhesion characteristics, rapid rate of curing, low-temperature curing characteristics, and the high strengeh exhibited by the fully cured resin. As will be appreciated by those skilled in the art, epoxy resins in the liquid state can be referred to as prepolymers in which the number of repeating units of the polymer is low enough such that the resin flows readily during preparation of side A. A nurmber of epoxy resins may be suitable for use in formulating side A, including epoxy novolak resin, cycloaliphatic epoxide resin, aliphatic epoxy resin, and other similar epoxy resins. Most preferred is bisphenol A-epichlorohydrine resin. A suitable bisphenol A-epichlorohydrine resin is available under the trademark "Epi-Rez 510" from the Interez Corporation.
In addition to the aforementioned attributes, the preferred thermosetting resins of the present invention are both economical, have a low order of shrinkage on cure, produce no cure byproducts, and have chemical and environmental resistance. The chemistry and polymerization reactions or curing mechanisms of the epoxy resins are well understood and thus their preparation will not be detailed.
!~ The unexpanded microspheres used in preparing side A of the present invention are preferably activated or expanded by thermal action. In addition to providing a lightweight reinforcement member due to their low density, the expandablc microsphcres function in the present invention as an expanding agent which, upon activation, C;IUSCS the reactive dough of the prescnt invention to "rise" or expand such that it fills the cavity in which it is d.sposed. By expanding in this manner, the reactivc dough makcs excellent contact with surrounding structures, filling any small voids and conforming to irregulnr surfaces. Unexpanded microsphcres are ~enerally organic in naturc and m~y be obtaincd from a numbcr of sources. The preferrcd uncxpandcd, :,, : .
` - 1 325496 1 992.02 1 thermally-expandable microspheres have an average diameter of approximately 5 rnicrons to about 7 microns which increases to about 40 microns to about 60 microns upon expansion. The preferred beads are thermally activated by the he~t generated in the exothermic polymerization reaction in which the therrnosetting resin of side or part A
thus should expand at temperatures between about 100 degrees C to about 120 degrees C.
Two particularly preferred types of unexpanded, thermally-expandable polyvinylidcne chloride microspheres are those sold under the trademark "Expancel 551-DU" sold by the Expancel Corporation. Other equivalent expandable rnicrospheres which sre suitable ' for use in the present invention will be known to those skilled in the art. Unexpanded, thermally-expandable microspheres comprise from about .1% by weight to about 20% by weight, preferably from about .5% by weight to about 10% by weight, and most preferably from about 1% by weight to about 3% by weight of side A of the present nvention.
~,j In order to add bulk to the first composition, to extend the thermosetting resin, and to give the first composition its dough-like consistency, a filler is added along with the unexpanded, thermally-expanded microspheres. It is to be understood that the exac~ order in which the three components of part A are blended :, together is not critical, although it is preferred that the dry constituents, that is, the ~3 filler and unexpanded, thermally-expandable microspheres, be added slowly to the epoxy `J resin. Also, if the ranges set forth for the three constituents in a given case do not .1 `~ provide the op~imum dough-like consistency, the viscosity of the dough is most easily adJusted by adjusting the amount of filler which is used.
A number of fillers are suitable for use herein, alone or in combination with one another, such as calcium carbonate, talc (hydrated magnesium silicatc), and kaolinite (hydrated aluminum silicate). Various clays may be suitable.
',,~
Othcr fillers which m~y be useful in the present invention include alumina trihydratc, feldspar ~anhydrous alkal; alumina silicate), and silica. Solid glass sphercs could bc uscd, although they are not necessarily beneficial in tcrms of density. Most prefcrrcd ..'~
~i for usc hcrcin ~rc hollow glass spheres, also known as glass bubbles or glass balloons, having an avcrage diamcter less than about 70 microns. Thcse hollow glass .' ::
:, . , ., .
- 1 3254q6 1 992.02 1 microsphcres are preferred due to their low density and high strength. While multicellular hollow microspheres may be suitable, the unicellular type are known to work well. Also, organic hollow microspheres may be a suitable filler. These hollow microsphercs may be used in combination with miner~l fillers to make up the total concentratiort of filler. Filler comprises from about .5% to about 90% by weight, preferably from about 5% to ~bout 60% by weight and most prefcrably from about 20%
to 30% by weight of part A.
Referring again to Figure 4 of the drawings, the next step of the present invention is the preparation of the second composition or part B. Part or side B
includes a curing agent or hardener as the active agent which must be compatible with the thermosetting resin which is used to formulate part A. That is~ the curing agent in part B must be capable of promoting cross-linking of the thermosetting resin which is used in the first composition. This is critical since the final reactive dough which is prepared by blending together part A and part B must undergo cross-linking to cure the thermosetting resin of part A. A number of curing agents will be known to those skilled in the art for this purpose. Both the nature of the curing agent and the concentration of curing agent used should in the final reactive dough promote a cross^linking reaction which is rapid and moderately exothermic to generate the heat necessa~y to expand the unexpanded, thermally-expandable microspheres. However, the rate of cure should not be so rapid that the reactive dough hardens before adequate time is allowed for it to bc hand-packed into a hollow structural member. Therefore~ and although this period may vary widely, it is preferred that the reactive dough which is formed by blendin~ together part A and part B of the presellt invention should remain fairly dough-like for a period of about thirty minutes after blending. This period will be adequate on most occasions.
Substantially full cure should be complete in about twenty-four hours.
Thercfore, a curing a&ent is present in part B at a concentration ot about 10% to about 90% by weight, preferably about 30% to about 85% by wcight, and ~, most prefcrably from about 60% to about 75% by wcight of part B. Where thc thermosctting resin of part A is an epoxy resin as preferrcd, suitable curing agents includc aliphatic amines and aliphatic poly~mincs such as primary polyamincs and I I -., . ~
1992.021 ~ 4 9 6 - ~ second~ry poly~mines, and polyanides. bl'et~yl'enetriamine and tricthyleDeletramine arc particularly prcferred. A particularly preferrcd cllring agent ror use in part B
'I where part A includes an epoxy resin is that sold under the ~rademark "Interez 826 H~rdener" avail~ble î rom the Interez Corporation. "Intercz 826 H~rdcner" is an aliphatic amine adduct partially re~cted with an epo~y re:sin. Aliphatic ~mido amines *
such as "Epicure 856" also available from Intcrez Corporation m~y also be suitJble.
Again, the second composition which is part or side B of the kit has ~
dough-likc consistency similar to the consistealcy of part A. This is achieved by adding to the curing agcnt, prefcrably a liquid or a solution, a quaneity of filler which is sufficicnt to raisç the ~iscosity of part B to a dough-like consistcncy. The same considerations generally applic~ble to selecting a filler for part A are cqually applic~ble for part B and the aforcmentioned list of fillers arc acceptable. Due to their excellcnt durability and density charactcristics, hollow glass microsph¢res arc preferred for use 35 fillcr in part ~. Particularly preferred are those hollow glass microspheres sold under the tradem~rk "3M C15" by the 3M Compa~y. F~llcr comprises from about .5% to about ~0% by weight, prcfcrably from about 109~ to abou~ 7Q% by wei~ht, and most preferably from about 20% to aboul 40% by wcight of part B. As stated~ it is ~hc ~ttainment of the dough-like consistency rather than thc spccific concentration of f;ller which is3 impor~ant in formulating part B.
, As prcviously explained, in ordcr to simplif y the process of determining when pare A and part B have bee~ uniformly mixcd or blendcd together, a color~nt is addcd to cithor part A or part B. 1~ is preferrcd that the coloraDt be added to part B. The addition of the colorant to part B is preferred sincc, as will be shown, p~rt A ~nd part B re proYidcd ;n thc final reac~iYc dough In a volumetric rstio of abou~ four parts to about one part. That is, about four to five parts of p~rt A are addcd to about one p2rt of part B. By providing ~he color~nt in the dough of lesser volume, more 3~ blending will gener~lly bc required ~o re~ch a unirorm color which gives gre3tcr assur~ncc Or uni~orm mixing. Thc color~nts which ~re prcferrcd for use in the prescn~
invcntion c~n bc eithcr dyes or pigments ~nd prefer~bly cornprise inorganic or organic ~, pigmcnt which is c~sily dispersiblc in part B. A number of hues ~re accept3ble, bul is *Trade Mark .', ~,.', .
.
, , - 1 3 ~ 5 4 9 6 1 992.Q2 1 preferred that black be used. Generally, the constituents of part A when mixed will provide a white dough. Thus, by coloring part B black, uniform blending is achieved when the reactive dough is uniformly gray. Thus, dyes such as nigrosines, for example, solvent black 5 or solvent black 7 may be used, and most preferably carbon black is used as the colorant in part B. Preferred are thermal and furnnce blacks which are outstanding colorants and which also protect the final reinforcement structure from ultraviolet degradation. The quantity of colorant which is used is that amoùnt sufficient to uniformly color part B. Typically, from about 0.05~b to about 10% by weight, preferably from about .1% to about 3% by weight and most preferably from-. about .5% to about 1.0% by weight of part B is added to part ~ as the colorant.
, The mixing sequence for part B is not critical, although it will usually include the slow addition of filler and carbon black to a liquid curing agent which is stirred and then kneaded to its dough-like consistency.
,~
A number of other ingredients can be used to further enhance the ~' properties of the present invention. For example, a coupiing agent can be added to part ;' A to modify the interface of the thermosetting resin matrix and an inorganic filler such . that a more solid structure is attained. A coupling agent where utilized would typically ~, be included in part B, that is, the second composition. Suitable coupling agents include silanes such as gama-chloropropyl-trimethoxysilane or tritanates such as isopropyl-tri(dioctylpyrophosphate)titanate. Certain accelerators may be useful in ~art B to , increase the activity of the curing agent in promoting cross-linking of the thermosetting resin.
.
.1 Other additives such as anti-oxidants or fibrous reinforcement matcrials may be useful. Suitable fibrous reinforcements may include chopped aramid fibers, choppcd carbon fibers, chopped glass strnins and millcd glass fibers. The concentrations of thcse materials may vaiy so long as the desircd durability of thc final ;~ reinforccment membcr, workability of the reactive dough and the othcr objects of the ~ present invention arc achicvcd.
., ~
1 992.02 1 Referring now to Figures 2 and 4 of the drawings, region or section 26 is prepared for reinforcement by the present inverltion in the following manner. First, cavity or channel 36 is exposed such that reinforcement member 34 can be formed in place. Thus, the next step of the present invention is the preparation of the hollow structural membcr to receive the reactive dough. As stated, although the present invention is suitable for use in reinforcing plastic structural members, it is anticipated that the primary application of the present invention will be for use in reinforcing metal hollow structural members which have been damaged, such as in a collision. The surfaces of U-shaped stamping 30, which will be in contact with reinforcement member 34, are cleaned for good contact and adhesion by the reactive dough. This cleaning process may include blowing off excess dirt and dust and preferably includes a brief wash with acetone or alcohol. Preferably, rust and any weld scale present should be removed. Once the surface of U-shaped stamping 30 has been prepared, the reactivc dough will be used to form reinforcement member 34 as prepared.
As stated, it is contemplated that the present invention will be made available as a kit and, referring now to Figure 5 of the drawings, kit 4$ is shown comprising container 50 having receptacles or cavities 52 and 54. Receptacles 50 and 54 are separated by partition 56. Container 50 is constructed of a material which is substantially non-reactive with respect to its contents. Receptacle 54 houses the first compos;t}on or part A 58 which is the thermosetting resin dough composition.
Receptacle 52 contains part B 60 which is the curing agent dough composition.
Substantially air-tight lid 62 is also provided.
In order to prepare the reactive dough, part A 58 and part B 60 are ~Icnded together uniformly. For the preferred compositions of part A 58 and part B 60, the two parts are blended together in the approximate ratio of bctween about four parts part A to about one part part B in parts by volume and five parts A to about one part B in parts by volume. That is, the volume of part A 58 which is blcnded with part B 60 is approximately four times greater than the volume of part B 60. Since part B 60 includes a colorant, preferably carbon black, uniformity of blending of ptlrt A and part B can be obscrvcd once the combincd or blended reactive dough has a uniform gr~y color. It !
,' , .
~"' ' , ' .
,'' ' ' , .
~ - 1 32549~
1 992.02 1 should bc pointed out that it may be desirable to add a pigment to part A such as titanium oxidc if the ingredients of part A yield a dough which is not white. Once part A and part B are blended together to form the reactive dough, a number of physical and chcmical changes occur. As the curing agent contacts the thermosetting resin, the polymerization or cross-linking of the thermosetting resin is promoted in the process of curing the thermosetting resin. As the thermosetting resin cures, the reactive dough will bccome even more viscous. The une~cpanded, ther nally-expandable microspheres, which are now uniformly distributed throughout the reactive dough, will begin toexpand in response to the heat generated during the exothermic cross-linking reaction.
! This expansion of the expandable microspheres causes the reactive dough to rise or expand. Thus, the next step of the invention is the packing of the reactive dough into i` cavity 36 in contact with U-shaped stamping 30 in region 26 to be reinforced.
Both the blending of part A and part B to form the reactis~e dough and the packing of the reactive dough into channel 36 are preferably performed by hand, although it may be possible to automate this procedure. When hand-blending and hand--~ packing, the repair person should use solvent- resistant gloves or the like so that direct contact between the reactive dough aDd the repair person's hands is not made. As `1 stated, the preferred compositions of the present invention produce a reactive dough which can be easily worked by hand for approximately thirty minutes, during which time the reactive dough continually rises or expands. The reactive dough should be packed into cavity 36 such that the area or region 26 to be reinforced is substantially .~ filled. Once the reactive dough has been packed into cavity 36, it is preferred that closure plate 32 be welded onto U-shaped stamping 30 such that the reactive dough is enclosed in cavity or channel 36. This may be accomplished most readi}y by spot welding closure plate 32 at flanges 38 and 40. It may be desirable to increase the rate of curing and expansion of the reactive dough by heating region 26 of U-shaped member 30 1~' Wittl a heat gun or thc likc prior to packing the reactive dough into channcl 36. Thc heat encrgy will not only incrcase the rate of the cross-linking reaction of thc thcrmosctting rcsin, but also will increasc the rate at which the thcrmally- cxpandablc microsphcrcs expnnd. Also, the heat gencrated during the welding, such as mig welding, of ctosurc plntc 32 on U-shaped stamping 30 ~t region 26 gener;llly also hcats thc reactive ~ ~ .
- 1 325~96 1 992.02 1 dough, enhancing its cure rate. As the reactive dough expands, it fills any small cracks, voids, or surface irregularities in region 26 of U-shaped stamping 30 and bonds by adhesion to U-shaped stamping 30 and closure plate 32. In approximately twenty-four hours, the reactive dough has substantially fully cross-linked and the thermally-expandable microspheres have substantially fully expanded such that reinforcement member 34 shown in Figure 2 is formed. Thus, thc last step of the invention is the attachment of closure plate 32 after wllich the reactive dough cures to form reinforcement member 34.
Reinforcement member 34 has good strength and energy absorption characteristics and in most instances will restore the original characteristics of the damagcd part which has been repaired and reinforced by the present invention. Due to the compositional characteristics of reinforcement member 34, and due to its expansion in channel 36, acoustical dampening is achieved which eliminates any rattle or the like by cover plate 32. A mating section of U-shaped stamping 28 may then be welded onto cover plate 32 if desired. Reinforcement member 3~ also provides good corrosion resistance which is a significant problem in prior art metal plate reinforcing techniques.
In addition, a heat lamp or the like may be emplo~ed to facilitate the cure of the reactive dough and expansion of the microspheres, if desired.
The present invention may be used to reinforce hollow sections other than vehicle frames or the like~ including boat hulls or other structures where a Iightweight, strong reinforcement is desired or in automotlve roof structures such as the ;~pillars. Kit 48 is both convenient and easy to implement and requires no comple:c ~imixing of hazardous materials nor does it require exact measurements or temperature rnnges to be observed.
, - 1 6--1 992.02 1 While a particular embodiment of this invention is shown and described herein, it will be understood, of course, that the inYention is not to be limited thereto since many modifications may be made, particularly by those skilled in the art, in light of this disclosure. It is contemplated therefore by the appended claims to cover any such modifications as fall within the true spirit and scope of this invention.
The following example further illustrates the method of making and using the present invention and is not intended to in any way limit the scope of this invention i EXAMPLE
A two-part system was prepared in accordance with the procedures and parameters set forth in the foregoing description of the preferred embodiments as 3 follows. ''3MC15" microspheres and "Expancel 551-DU" were added slowly to "Interez 510" epoxy, and the composition was stirred and then kneaded to a dough-like consistency. This was carried out at ambient temperature and pressure to yield adough-like composition or part A having the following compositional make-up:
~L~
;l Interez 510 Epoxy 73.0 parts by weight 3 3M C15 Microspheres 25.5 parts by weight Expancel S5 1 -DU 1.5 parts by weigh~
Part A was then placed in a closed container for later use.
'1 Part B was prepared, again at ambient temperature and pressure, by slowly adding 3M C15 microspheres and carbon black to "Interez 826" hardener. The ingredients wcrc mixcd and then kneaded to a dough-like consistency. P~rt B had tllc following compositional make-up:
. .
fl, ,~,, ., . . .
; :
I 992.02 1 Part B
Interez 826 Hardener 69.4 parts by weight 3M C 15 Microspheres 30.0 parts by weight Carbon Black 0.6 parts by weight The dough-like part B was then placed in a closed container for subsequent use.
.
, Four parts by volume of part A were then blended by kneading with one part by volume of part B until the reactive dough so formed had a uniform gray :
appearance. The kneading process took only a few minutes, and the reactive dough was then packed into a C-section to be reinforced. The channel of the C-section was then closed with a closure plate, and the dough was allowed to rise in place. In approximately twenty-four hours, the reactive dough had fully cured to form a reinforcement member. The reinforced (:-section exhibited good strength ~ .
i~ characteristics.
,, .
' ,, .
., .~
~ ., `I;
,.
.~ .
. 1 '.~
, . ~
. ...
~il ri , .
,. ..
;
i~
: ~' - 1 8-;
.:
., -, ,, :
Claims (19)
1. A two-part kit for reinforcing a hollow structural member comprising:
a pre-measured quantity of a first composition;
a pre-measured quantity of a second composition;
said first composition including from about 5 to about 99 percent by weight thermosetting resin and from about 0.1 to about 20 percent by weight unexpanded, thermally-expandable microspheres;
said second composition including from about 10 to about 90 percent by weight curing agent adapted to promote cross-linking polymerization of said thermosetting resin in an exothermic reaction, said unexpanded, thermally expandable microspheres being adapted to expand due to the heat generated by said exothermic reaction without the application of heat from an external heat source;
said first composition further having from about 0.5 to about 90 percent by weight filler to provide a doughy consistency to said first composition;
said second composition further having from about 0.5 to about 90 percent by weight filler to provide a doughy consistency to said second composition;
said first and second compositions being provided in said kit at a predetermined ratio to one another;
whereby the blending of said second composition with said first composition causes said curing agent to combine with said thermosetting resin to bring about said exothermic reaction of said thermosetting resin, and wherein heat evolved during said exothermic reaction causes said thermally-expandable microspheres to expand as said thermosetting resin cures.
a pre-measured quantity of a first composition;
a pre-measured quantity of a second composition;
said first composition including from about 5 to about 99 percent by weight thermosetting resin and from about 0.1 to about 20 percent by weight unexpanded, thermally-expandable microspheres;
said second composition including from about 10 to about 90 percent by weight curing agent adapted to promote cross-linking polymerization of said thermosetting resin in an exothermic reaction, said unexpanded, thermally expandable microspheres being adapted to expand due to the heat generated by said exothermic reaction without the application of heat from an external heat source;
said first composition further having from about 0.5 to about 90 percent by weight filler to provide a doughy consistency to said first composition;
said second composition further having from about 0.5 to about 90 percent by weight filler to provide a doughy consistency to said second composition;
said first and second compositions being provided in said kit at a predetermined ratio to one another;
whereby the blending of said second composition with said first composition causes said curing agent to combine with said thermosetting resin to bring about said exothermic reaction of said thermosetting resin, and wherein heat evolved during said exothermic reaction causes said thermally-expandable microspheres to expand as said thermosetting resin cures.
2. The kit for reinforcing a hollow structural member recited in claim 1, wherein said second composition includes a colorant having a first hue and said first composition has a second hue, such that said addition of said second composition to said first composition produces a third composition having a third hue which is intermediate between said first and second hue.
3. The kit for reinforcing a hollow structural member recited in claim 1, wherein said thermosetting resin is an epoxy resin.
4. The kit for reinforcing a hollow structural member recited in claim 3 wherein said epoxy resin is bisphenol A-epichlorohydrin resin.
5. The kit for reinforcing a hollow structural member recited in claim 3, wherein said epoxy resin is an epoxy novolak resin.
6. The kit for reinforcing a hollow structural member recited in claim 3, wherein said epoxy resin is a cycloaliphatic epoxide resin.
7. The kit for reinforcing a hollow structural member recited in claim 3, wherein said epoxy resin is an aliphatic epoxy resin.
8. The kit for reinforcing a hollow structural member recited in claim 1, wherein said curing agent is an aliphatic amine.
9. The kit for reinforcing a hollow structural member recited in claim 8, wherein said aliphatic amine is selected from the group consisting of primary polyamines, secondary polyamines, and polyamides.
10. The kit for reinforcing a hollow structural member recited in claim 8, wherein said aliphatic amine is selected from the group consisting of diethylenetriamine and triethylenetetramine.
11. The kit for reinforcing a hollow structural member recited in claim 3, wherein said first composition includes a fibrous reinforcement material selected from the group consisting of chopped aramid fibers, chopped carbon fiber, chopped glass strands, and milled glass fibers and combinations thereof.
12. The kit for reinforcing a hollow structural member recited in claim 1, wherein said second composition includes a fibrous reinforcement material selected from the group consisting of chopped aramid fibers, chopped carbon fiber, chopped glass strands and milled glass fibers and combinations thereof.
13. The kit for reinforcing a hollow structural member recited in claim 1, wherein said second composition includes a coupling agent.
14. The kit for reinforcing a hollow structural member recited is claim 2, wherein said colorant is carbon black.
15. A two-part kit for preparing a composition to be used in reinforcing a hollow structural member comprising:
a pre-measured quantity of a first dough having from about 5 to about 99 percent by weight of a thermosetting resin, from about 0.5 to about 90 percent by weight of a first filler and from about 0.1 to about 20 percent by weight of an unexpanded, thermally-expandable microspheres;
a pre-measured quantity of a second dough having from about 10 to about 90 percent by weight of a curing agent and from about 0.5 to about 90 percent by weight of a second filler, said curing agent being adapted to cross-link said thermosetting resin in an exothermic reaction;
said unexpanded, thermally-expandable microspheres being adapted to expand upon thermal activation by the heat of said exothermic reaction without the application of heat from an external heat source;
from about 0.05 to about 10 percent by weight of a colorant in admixture with one of said first and second doughs wherein said one of said first and second doughs having said colorant has a hue different, than said other of said first and second doughs;
said first and second doughs being provided in a predetermined ratio to one another;
whereby the blending together of said first and second doughs provides a composition having a hue different than either of said first and second doughs and whereby said curing agent combines with said thermosetting resin to cause said exothermic reaction of said thermosetting resin, and wherein heat evolved by said exothermic reaction activates said thermally-expandable microspheres to expand as said thermosetting resin cures.
a pre-measured quantity of a first dough having from about 5 to about 99 percent by weight of a thermosetting resin, from about 0.5 to about 90 percent by weight of a first filler and from about 0.1 to about 20 percent by weight of an unexpanded, thermally-expandable microspheres;
a pre-measured quantity of a second dough having from about 10 to about 90 percent by weight of a curing agent and from about 0.5 to about 90 percent by weight of a second filler, said curing agent being adapted to cross-link said thermosetting resin in an exothermic reaction;
said unexpanded, thermally-expandable microspheres being adapted to expand upon thermal activation by the heat of said exothermic reaction without the application of heat from an external heat source;
from about 0.05 to about 10 percent by weight of a colorant in admixture with one of said first and second doughs wherein said one of said first and second doughs having said colorant has a hue different, than said other of said first and second doughs;
said first and second doughs being provided in a predetermined ratio to one another;
whereby the blending together of said first and second doughs provides a composition having a hue different than either of said first and second doughs and whereby said curing agent combines with said thermosetting resin to cause said exothermic reaction of said thermosetting resin, and wherein heat evolved by said exothermic reaction activates said thermally-expandable microspheres to expand as said thermosetting resin cures.
16. The kit for preparing a composition to be used in reinforcing a hollow structural member recited in claim 15, wherein said thermosetting resin is an epoxy resin.
17. The kit for preparing a composition to be used in reinforcing a hollow structural member recited in claim 15, wherein said curing agent includes means for curing an epoxy resin.
18. The kit for preparing a composition to be used in reinforcing a hollow structural member recited in claim 15, wherein said colorant is carbon black.
19. The kit for preparing a composition to be used in reinforcing a hollow structural member recited in claim 15, wherein said first and second fillers are hollow microspheres.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/166,282 | 1988-03-10 | ||
| US07/166,282 US4923902A (en) | 1988-03-10 | 1988-03-10 | Process and compositions for reinforcing structural members |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1325496C true CA1325496C (en) | 1993-12-21 |
Family
ID=22602607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000592960A Expired - Lifetime CA1325496C (en) | 1988-03-10 | 1989-03-07 | Process and compositions for reinforcing structural members |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4923902A (en) |
| CA (1) | CA1325496C (en) |
| WO (1) | WO1989008678A1 (en) |
Families Citing this family (150)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5124186A (en) * | 1990-02-05 | 1992-06-23 | Mpa Diversified Products Co. | Composite tubular door beam reinforced with a reacted core localized at the mid-span of the tube |
| US4978562A (en) * | 1990-02-05 | 1990-12-18 | Mpa Diversified Products, Inc. | Composite tubular door beam reinforced with a syntactic foam core localized at the mid-span of the tube |
| GB2254055B (en) * | 1991-03-28 | 1995-04-05 | Bothwell P W | Vehicle |
| US5470886A (en) * | 1994-03-31 | 1995-11-28 | Ppg Industries, Inc. | Curable, sprayable compositions for reinforced thin rigid plates |
| US5575526A (en) * | 1994-05-19 | 1996-11-19 | Novamax Technologies, Inc. | Composite laminate beam for radiator support |
| US6168226B1 (en) | 1994-05-19 | 2001-01-02 | Henkel Corporation | Composite laminate automotive structures |
| GB2291426B (en) * | 1994-07-19 | 1998-05-06 | Sumitomo Chemical Co | Epoxy resin composition process for producing the same and resin-sealed semiconductor device |
| US6165588A (en) * | 1998-09-02 | 2000-12-26 | Henkel Corporation | Reinforcement of hollow sections using extrusions and a polymer binding layer |
| US5755486A (en) * | 1995-05-23 | 1998-05-26 | Novamax Technologies Holdings, Inc. | Composite structural reinforcement member |
| US6270600B1 (en) | 1996-07-03 | 2001-08-07 | Henkel Corporation | Reinforced channel-shaped structural member methods |
| US5888600A (en) * | 1996-07-03 | 1999-03-30 | Henkel Corporation | Reinforced channel-shaped structural member |
| US6482496B1 (en) | 1996-07-03 | 2002-11-19 | Henkel Corporation | Foil backed laminate reinforcement |
| DE19707462C1 (en) * | 1997-02-25 | 1998-06-18 | Bayerische Motoren Werke Ag | Armoured road vehicle with reinforced bodywork chassis parts |
| US6461691B1 (en) * | 1997-05-21 | 2002-10-08 | Denovus Llc | Curable sealant composition |
| US6277898B1 (en) * | 1997-05-21 | 2001-08-21 | Denovus Llc | Curable sealant composition |
| US6858260B2 (en) | 1997-05-21 | 2005-02-22 | Denovus Llc | Curable sealant composition |
| US6479560B2 (en) * | 1997-05-21 | 2002-11-12 | Denovus Llc | Foaming compositions and methods for making and using the composition |
| US6174932B1 (en) * | 1998-05-20 | 2001-01-16 | Denovus Llc | Curable sealant composition |
| US6444713B1 (en) * | 1997-05-21 | 2002-09-03 | Denovus Llc | Foaming compositions and methods for making and using the compositions |
| US6237304B1 (en) | 1997-07-18 | 2001-05-29 | Henkel Corporation | Laminate structural bulkhead |
| US6233826B1 (en) | 1997-07-21 | 2001-05-22 | Henkel Corp | Method for reinforcing structural members |
| US6096403A (en) * | 1997-07-21 | 2000-08-01 | Henkel Corporation | Reinforced structural members |
| US6451231B1 (en) | 1997-08-21 | 2002-09-17 | Henkel Corporation | Method of forming a high performance structural foam for stiffening parts |
| WO1999015582A1 (en) * | 1997-09-22 | 1999-04-01 | Siemens Aktiengesellschaft | Duro-plastic composite material with expandable hollow microspheres and use of the same for encapsulation |
| US6103341A (en) | 1997-12-08 | 2000-08-15 | L&L Products | Self-sealing partition |
| US6068424A (en) * | 1998-02-04 | 2000-05-30 | Henkel Corporation | Three dimensional composite joint reinforcement for an automotive vehicle |
| US20030195268A1 (en) * | 1998-05-20 | 2003-10-16 | Freitag James W. | Novel foaming compositions and methods for making and using the composition |
| US5992923A (en) * | 1998-05-27 | 1999-11-30 | Henkel Corporation | Reinforced beam assembly |
| EP0982364A1 (en) * | 1998-08-25 | 2000-03-01 | Nicolas Bitar | Epoxy putty reinforced with aramid fibers and containing a gel coat |
| ZA991856B (en) | 1998-08-27 | 1999-09-22 | Henkel Corp | Storage-stable compositions useful for the production of structural foams. |
| US6103784A (en) * | 1998-08-27 | 2000-08-15 | Henkel Corporation | Corrosion resistant structural foam |
| US6376564B1 (en) * | 1998-08-27 | 2002-04-23 | Henkel Corporation | Storage-stable compositions useful for the production of structural foams |
| US6387470B1 (en) | 1998-11-05 | 2002-05-14 | Sika Corporation | Sound deadening and structural reinforcement compositions and methods of using the same |
| US7632559B2 (en) * | 1998-11-05 | 2009-12-15 | Sika Technology Ag | Sound deadening and structural reinforcement compositions and methods of using the same |
| US6276105B1 (en) | 1999-01-11 | 2001-08-21 | Henkel Corporation | Laminate reinforced beam with tapered polymer layer |
| US6110982A (en) * | 1999-01-13 | 2000-08-29 | Sandia Corporation | Epoxy foams using multiple resins and curing agents |
| US6189953B1 (en) * | 1999-01-25 | 2001-02-20 | Henkel Corporation | Reinforced structural assembly |
| US6092864A (en) * | 1999-01-25 | 2000-07-25 | Henkel Corporation | Oven cured structural foam with designed-in sag positioning |
| US6149227A (en) * | 1999-01-25 | 2000-11-21 | Henkel Corporation | Reinforced structural assembly |
| DE19909270A1 (en) | 1999-03-03 | 2000-09-07 | Henkel Teroson Gmbh | Thermosetting, thermally expandable molded body |
| US6131897A (en) | 1999-03-16 | 2000-10-17 | L & L Products, Inc. | Structural reinforcements |
| US6207730B1 (en) | 1999-03-18 | 2001-03-27 | Daubert Chemical Company, Inc. | Epoxy and microsphere adhesive composition |
| JP5133482B2 (en) * | 1999-07-21 | 2013-01-30 | イムデ ビオマテリオー | Adhesive protein foam for surgical and / or therapeutic use, and methods and kits for its production |
| US6358584B1 (en) | 1999-10-27 | 2002-03-19 | L&L Products | Tube reinforcement with deflecting wings and structural foam |
| USH2047H1 (en) | 1999-11-10 | 2002-09-03 | Henkel Corporation | Reinforcement laminate |
| US6668457B1 (en) | 1999-12-10 | 2003-12-30 | L&L Products, Inc. | Heat-activated structural foam reinforced hydroform |
| US6263635B1 (en) | 1999-12-10 | 2001-07-24 | L&L Products, Inc. | Tube reinforcement having displaceable modular components |
| US6199940B1 (en) | 2000-01-31 | 2001-03-13 | Sika Corporation | Tubular structural reinforcing member with thermally expansible foaming material |
| US6253524B1 (en) | 2000-01-31 | 2001-07-03 | Sika Corporation | Reinforcing member with thermally expansible structural reinforcing material and directional shelf |
| US6305136B1 (en) | 2000-01-31 | 2001-10-23 | Sika Corporation | Reinforcing member with beam shaped carrier and thermally expansible reinforcing material |
| US6475577B1 (en) | 2000-02-07 | 2002-11-05 | Sika Corporation | Reinforcing member with intersecting support legs |
| EP1265778B1 (en) | 2000-02-11 | 2016-10-05 | Zephyros Inc. | Structural reinforcement system for automotive vehicles |
| US6467834B1 (en) | 2000-02-11 | 2002-10-22 | L&L Products | Structural reinforcement system for automotive vehicles |
| US6296298B1 (en) | 2000-03-14 | 2001-10-02 | L&L Products, Inc. | Structural reinforcement member for wheel well |
| US6482486B1 (en) | 2000-03-14 | 2002-11-19 | L&L Products | Heat activated reinforcing sleeve |
| US6422575B1 (en) | 2000-03-14 | 2002-07-23 | L&L Products, Inc. | Expandable pre-formed plug |
| US6321793B1 (en) | 2000-06-12 | 2001-11-27 | L&L Products | Bladder system for reinforcing a portion of a longitudinal structure |
| US6820923B1 (en) | 2000-08-03 | 2004-11-23 | L&L Products | Sound absorption system for automotive vehicles |
| US6620501B1 (en) | 2000-08-07 | 2003-09-16 | L&L Products, Inc. | Paintable seal system |
| US6634698B2 (en) | 2000-08-14 | 2003-10-21 | L&L Products, Inc. | Vibrational reduction system for automotive vehicles |
| US6494525B1 (en) | 2000-09-15 | 2002-12-17 | Sika Corporation | Side impact reinforcement |
| US6403222B1 (en) | 2000-09-22 | 2002-06-11 | Henkel Corporation | Wax-modified thermosettable compositions |
| US6561571B1 (en) | 2000-09-29 | 2003-05-13 | L&L Products, Inc. | Structurally enhanced attachment of a reinforcing member |
| US6471285B1 (en) | 2000-09-29 | 2002-10-29 | L&L Products, Inc. | Hydroform structural reinforcement system |
| US6451876B1 (en) | 2000-10-10 | 2002-09-17 | Henkel Corporation | Two component thermosettable compositions useful for producing structural reinforcing adhesives |
| US6585202B2 (en) | 2001-01-05 | 2003-07-01 | Daimlerchrysler Corporation | Multi-tiered carrier structure for a motor vehicle |
| GB0106911D0 (en) * | 2001-03-20 | 2001-05-09 | L & L Products | Structural foam |
| US20030018095A1 (en) * | 2001-04-27 | 2003-01-23 | Agarwal Rajat K. | Thermosettable compositions useful for producing structural adhesive foams |
| US6787579B2 (en) * | 2001-05-02 | 2004-09-07 | L&L Products, Inc. | Two-component (epoxy/amine) structural foam-in-place material |
| US7473715B2 (en) * | 2001-05-02 | 2009-01-06 | Zephyros, Inc. | Two component (epoxy/amine) structural foam-in-place material |
| GB2375328A (en) * | 2001-05-08 | 2002-11-13 | L & L Products | Reinforcing element for hollow structural member |
| US6502821B2 (en) | 2001-05-16 | 2003-01-07 | L&L Products, Inc. | Automotive body panel damping system |
| US6855652B2 (en) | 2001-08-24 | 2005-02-15 | L&L Products, Inc. | Structurally reinforced panels |
| US6682818B2 (en) * | 2001-08-24 | 2004-01-27 | L&L Products, Inc. | Paintable material |
| US20030050352A1 (en) * | 2001-09-04 | 2003-03-13 | Symyx Technologies, Inc. | Foamed Polymer System employing blowing agent performance enhancer |
| US6729425B2 (en) | 2001-09-05 | 2004-05-04 | L&L Products, Inc. | Adjustable reinforced structural assembly and method of use therefor |
| US6887914B2 (en) * | 2001-09-07 | 2005-05-03 | L&L Products, Inc. | Structural hot melt material and methods |
| US6730713B2 (en) * | 2001-09-24 | 2004-05-04 | L&L Products, Inc. | Creation of epoxy-based foam-in-place material using encapsulated metal carbonate |
| US6890964B2 (en) * | 2001-09-24 | 2005-05-10 | L&L Products, Inc. | Homopolymerized epoxy-based form-in-place material |
| US6786533B2 (en) * | 2001-09-24 | 2004-09-07 | L&L Products, Inc. | Structural reinforcement system having modular segmented characteristics |
| US6793274B2 (en) * | 2001-11-14 | 2004-09-21 | L&L Products, Inc. | Automotive rail/frame energy management system |
| US7041355B2 (en) | 2001-11-29 | 2006-05-09 | Dow Global Technologies Inc. | Structural reinforcement parts for automotive assembly |
| EP1456286B1 (en) | 2001-12-21 | 2012-06-13 | Henkel AG & Co. KGaA | Expandable epoxy resin-based systems modified with thermoplastic polymers |
| US6774171B2 (en) | 2002-01-25 | 2004-08-10 | L&L Products, Inc. | Magnetic composition |
| US7043815B2 (en) * | 2002-01-25 | 2006-05-16 | L & L Products, Inc. | Method for applying flowable materials |
| US7318873B2 (en) | 2002-03-29 | 2008-01-15 | Zephyros, Inc. | Structurally reinforced members |
| US6846559B2 (en) * | 2002-04-01 | 2005-01-25 | L&L Products, Inc. | Activatable material |
| BR0309088A (en) * | 2002-04-15 | 2005-02-09 | Dow Global Technologies Inc | Improved vehicular structural members and method for manufacturing such members |
| US6969551B2 (en) * | 2002-04-17 | 2005-11-29 | L & L Products, Inc. | Method and assembly for fastening and reinforcing a structural member |
| US7169344B2 (en) * | 2002-04-26 | 2007-01-30 | L&L Products, Inc. | Method of reinforcing at least a portion of a structure |
| US7077460B2 (en) | 2002-04-30 | 2006-07-18 | L&L Products, Inc. | Reinforcement system utilizing a hollow carrier |
| GB0211287D0 (en) * | 2002-05-17 | 2002-06-26 | L & L Products Inc | Improved baffle precursors |
| GB0211268D0 (en) * | 2002-05-17 | 2002-06-26 | L & L Products Inc | Hole plugs |
| GB0211775D0 (en) * | 2002-05-23 | 2002-07-03 | L & L Products Inc | Multi segment parts |
| AUPS323802A0 (en) * | 2002-06-27 | 2002-07-18 | University Of Newcastle Research Associates Limited, The | Toughening of thermosets |
| US6864297B2 (en) * | 2002-07-22 | 2005-03-08 | University Of Southern California | Composite foam made from polymer microspheres reinforced with long fibers |
| US6920693B2 (en) * | 2002-07-24 | 2005-07-26 | L&L Products, Inc. | Dynamic self-adjusting assembly for sealing, baffling or structural reinforcement |
| US7004536B2 (en) * | 2002-07-29 | 2006-02-28 | L&L Products, Inc. | Attachment system and method of forming same |
| US20040034982A1 (en) * | 2002-07-30 | 2004-02-26 | L&L Products, Inc. | System and method for sealing, baffling or reinforcing |
| US6923499B2 (en) * | 2002-08-06 | 2005-08-02 | L & L Products | Multiple material assembly for noise reduction |
| US6811864B2 (en) * | 2002-08-13 | 2004-11-02 | L&L Products, Inc. | Tacky base material with powder thereon |
| US20040076831A1 (en) * | 2002-10-02 | 2004-04-22 | L&L Products, Inc. | Synthetic material and methods of forming and applying same |
| US6883858B2 (en) * | 2002-09-10 | 2005-04-26 | L & L Products, Inc. | Structural reinforcement member and method of use therefor |
| US7105112B2 (en) * | 2002-11-05 | 2006-09-12 | L&L Products, Inc. | Lightweight member for reinforcing, sealing or baffling |
| GB0300159D0 (en) * | 2003-01-06 | 2003-02-05 | L & L Products Inc | Improved reinforcing members |
| DE10302298A1 (en) | 2003-01-22 | 2004-08-05 | Henkel Kgaa | Heat-curable, thermally expandable composition with a high degree of expansion |
| US7313865B2 (en) | 2003-01-28 | 2008-01-01 | Zephyros, Inc. | Process of forming a baffling, sealing or reinforcement member with thermoset carrier member |
| US20040204551A1 (en) * | 2003-03-04 | 2004-10-14 | L&L Products, Inc. | Epoxy/elastomer adduct, method of forming same and materials and articles formed therewith |
| US7111899B2 (en) * | 2003-04-23 | 2006-09-26 | L & L Products, Inc. | Structural reinforcement member and method of use therefor |
| US7125461B2 (en) * | 2003-05-07 | 2006-10-24 | L & L Products, Inc. | Activatable material for sealing, baffling or reinforcing and method of forming same |
| GB2401349A (en) * | 2003-05-08 | 2004-11-10 | L & L Products | Reinforcement for a vehicle panel |
| US7041193B2 (en) * | 2003-05-14 | 2006-05-09 | L & L Products, Inc. | Method of adhering members and an assembly formed thereby |
| US7199165B2 (en) * | 2003-06-26 | 2007-04-03 | L & L Products, Inc. | Expandable material |
| US20050016807A1 (en) * | 2003-07-21 | 2005-01-27 | L&L Products, Inc. | Crash box |
| US7469459B2 (en) * | 2003-09-18 | 2008-12-30 | Zephyros, Inc. | System and method employing a porous container for sealing, baffling or reinforcing |
| US20050102815A1 (en) * | 2003-11-03 | 2005-05-19 | L&L Products, Inc. | Reinforced members formed with absorbent mediums |
| US20050127145A1 (en) * | 2003-11-20 | 2005-06-16 | L&L Products, Inc. | Metallic foam |
| US20050166532A1 (en) * | 2004-01-07 | 2005-08-04 | L&L Products, Inc. | Structurally reinforced panels |
| US20050159531A1 (en) * | 2004-01-20 | 2005-07-21 | L&L Products, Inc. | Adhesive material and use therefor |
| US7180027B2 (en) * | 2004-03-31 | 2007-02-20 | L & L Products, Inc. | Method of applying activatable material to a member |
| US20050221046A1 (en) * | 2004-04-01 | 2005-10-06 | L&L Products, Inc. | Sealant material |
| US20050230027A1 (en) * | 2004-04-15 | 2005-10-20 | L&L Products, Inc. | Activatable material and method of forming and using same |
| US20050241756A1 (en) * | 2004-04-28 | 2005-11-03 | L&L Products, Inc. | Adhesive material and structures formed therewith |
| US8070994B2 (en) | 2004-06-18 | 2011-12-06 | Zephyros, Inc. | Panel structure |
| GB2415658A (en) * | 2004-06-21 | 2006-01-04 | L & L Products Inc | An overmoulding process |
| US7521093B2 (en) * | 2004-07-21 | 2009-04-21 | Zephyros, Inc. | Method of sealing an interface |
| US7838589B2 (en) * | 2004-07-21 | 2010-11-23 | Zephyros, Inc. | Sealant material |
| US20060021697A1 (en) * | 2004-07-30 | 2006-02-02 | L&L Products, Inc. | Member for reinforcing, sealing or baffling and reinforcement system formed therewith |
| US20060210736A1 (en) * | 2004-08-05 | 2006-09-21 | Wycech Joseph S | Method for forming a tangible item and a tangible item which is made by a method which allows the created tangible item to efficiently absorb energy |
| US7374219B2 (en) * | 2004-09-22 | 2008-05-20 | Zephyros, Inc. | Structural reinforcement member and method of use therefor |
| US20060090343A1 (en) * | 2004-10-28 | 2006-05-04 | L&L Products, Inc. | Member for reinforcing, sealing or baffling and reinforcement system formed therewith |
| US7503620B2 (en) * | 2005-05-12 | 2009-03-17 | Zephyros, Inc. | Structural reinforcement member and method of use therefor |
| US7926179B2 (en) | 2005-08-04 | 2011-04-19 | Zephyros, Inc. | Reinforcements, baffles and seals with malleable carriers |
| US7484946B2 (en) * | 2005-08-19 | 2009-02-03 | Zephyros, Inc. | Method and assembly for locating material within a structure |
| US8475694B2 (en) * | 2005-10-25 | 2013-07-02 | Zephyros, Inc. | Shaped expandable material |
| GB0600901D0 (en) * | 2006-01-17 | 2006-02-22 | L & L Products Inc | Improvements in or relating to reinforcement of hollow profiles |
| US7438782B2 (en) * | 2006-06-07 | 2008-10-21 | Zephyros, Inc. | Activatable material for sealing, baffling or reinforcing and method of forming same |
| US8288447B2 (en) * | 2006-06-07 | 2012-10-16 | Henkel Ag & Co. Kgaa | Foamable compositions based on epoxy resins and polyesters |
| US7820002B2 (en) * | 2006-11-16 | 2010-10-26 | Wycech Joseph S | Method for making a reception assembly and an reception assembly |
| US20080191378A1 (en) * | 2007-02-14 | 2008-08-14 | Brian Paul | Microsphere reinforcement of composite materials |
| DE102007032631A1 (en) | 2007-07-11 | 2009-01-15 | Henkel Ag & Co. Kgaa | Vehicle i.e. passenger car, body reinforcing method, involves hardening thermally hardenable mass introduced in some of segments of hollow space, where segments of hollow space filled with mass is reinforced |
| GB0806434D0 (en) * | 2008-04-09 | 2008-05-14 | Zephyros Inc | Improvements in or relating to structural adhesives |
| KR101637617B1 (en) * | 2008-07-29 | 2016-07-07 | 다우 글로벌 테크놀로지스 엘엘씨 | Toughened expandable epoxy resins for stiffening and energy dissipation in automotive cavities |
| GB0916205D0 (en) | 2009-09-15 | 2009-10-28 | Zephyros Inc | Improvements in or relating to cavity filling |
| US9096039B2 (en) | 2010-03-04 | 2015-08-04 | Zephyros, Inc. | Structural composite laminates |
| GB201016530D0 (en) | 2010-09-30 | 2010-11-17 | Zephyros Inc | Improvements in or relating to adhesives |
| GB201207481D0 (en) | 2012-04-26 | 2012-06-13 | Zephyros Inc | Applying flowable materials to synthetic substrates |
| US10577523B2 (en) | 2013-07-26 | 2020-03-03 | Zephyros, Inc. | Relating to thermosetting adhesive films |
| GB201417985D0 (en) | 2014-10-10 | 2014-11-26 | Zephyros Inc | Improvements in or relating to structural adhesives |
| DE102016206642A1 (en) * | 2016-04-20 | 2017-10-26 | Bayerische Motoren Werke Aktiengesellschaft | structural component |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL107364C (en) * | 1956-01-30 | 1900-01-01 | ||
| US2958905A (en) * | 1959-02-05 | 1960-11-08 | Dow Chemical Co | Method of fabricating expandable thermoplastic resinous material |
| US3373121A (en) * | 1962-02-12 | 1968-03-12 | Dow Chemical Co | Polyepoxide foam |
| US3322700A (en) * | 1964-04-22 | 1967-05-30 | Shell Oil Co | Method of foaming a resin composition comprising an epoxy resin, a vapor generating fluid, boron trifluoride catalyst and an ammonium halide |
| BE621501A (en) * | 1964-06-26 | 1900-01-01 | ||
| US3615972A (en) * | 1967-04-28 | 1971-10-26 | Dow Chemical Co | Expansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same |
| US3842020A (en) * | 1971-11-08 | 1974-10-15 | Dow Chemical Co | Method of expanding a resole resin containing expandable thermoplastic microspheres and product obtained therefrom |
| US3864181A (en) * | 1972-06-05 | 1975-02-04 | Pratt & Lambert Inc | Polymer foam compositions |
| GB1438703A (en) * | 1972-11-29 | 1976-06-09 | Gen Motors Corp | Energy-absorbing vehicle body end structure electrostatographic apparatus comprising a movable imaging |
| US3993608A (en) * | 1974-06-27 | 1976-11-23 | Minnesota Mining And Manufacturing Company | Poly(urethane-isocyanurate) foams containing hollow glass spheres |
| US4013810A (en) * | 1975-08-22 | 1977-03-22 | The Babcock & Wilcox Company | Sandwich panel construction |
| EP0021563B1 (en) * | 1979-04-20 | 1984-08-01 | The Secretary of State for Defence in Her Britannic Majesty's Government of the United Kingdom of Great Britain and | Resin materials, their use and article thereof |
| US4433068A (en) * | 1982-09-27 | 1984-02-21 | Long John V | Process for producing bonded macroballoon structures and resulting product |
| US4732806A (en) * | 1983-09-12 | 1988-03-22 | General Motors Corporation | Structural member comprising glass macrospheres |
-
1988
- 1988-03-10 US US07/166,282 patent/US4923902A/en not_active Expired - Lifetime
-
1989
- 1989-03-06 WO PCT/US1989/000906 patent/WO1989008678A1/en unknown
- 1989-03-07 CA CA000592960A patent/CA1325496C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US4923902A (en) | 1990-05-08 |
| WO1989008678A1 (en) | 1989-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1325496C (en) | Process and compositions for reinforcing structural members | |
| US4995545A (en) | Method of reinforcing a structure member | |
| US6706772B2 (en) | Two component (epoxy/amine) structural foam-in-place material | |
| JP4767477B2 (en) | Reinforcement for side impact | |
| US4908930A (en) | Method of making a torsion bar | |
| CA2346952C (en) | Method for filling and reinforcing honeycomb sandwich panels | |
| US6455126B1 (en) | Reinforcement of hollow sections using extrusions and a polymer binding layer | |
| AU711241B2 (en) | Composite structural reinforcement member | |
| US5124186A (en) | Composite tubular door beam reinforced with a reacted core localized at the mid-span of the tube | |
| WO1989010276A1 (en) | Filled tubular torsion bar and its method of manufacture | |
| EP1430093B1 (en) | Homopolymerized epoxy-based foam-in-place material | |
| CA2242860A1 (en) | Laminate structural bulkhead | |
| ITTO980631A1 (en) | PROCEDURE TO STRENGTHEN STRUCTURAL BODIES. | |
| GB2327387A (en) | Reinforced structural members | |
| CA2290423A1 (en) | Epoxy-containing foaming compositions and use thereof | |
| Kim et al. | Collapse characteristics of aluminum extrusions filled with structural foam for space frame vehicles | |
| JPH07113020A (en) | Resin composition of reduced weight | |
| JPH10139981A (en) | Epoxy resin composition for reinforcing car body, car body reinforcement structure, and method for reinforcing car body | |
| JP3651914B2 (en) | Two-part filling adhesive for model production or repair | |
| AU2001254804A1 (en) | Coherent insert | |
| Lawley | A review of adhesives in the automotive industry today | |
| JPS63297175A (en) | Forming method for automobile body hemming section | |
| JP2000085618A (en) | Rigidity improving method for foam filler and box-type member | |
| Nakajima et al. | A lightweight, multifunctional plastic reinforcement for body panels |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |