CA1257054A

CA1257054A - Flocced mineral materials and water-resistant articles materials made therefrom

Info

Publication number: CA1257054A
Application number: CA000497162A
Authority: CA
Inventors: Thomas M. Tymon
Original assignee: Armstrong World Industries Inc
Current assignee: Armstrong World Industries Inc
Priority date: 1985-03-25
Filing date: 1985-12-09
Publication date: 1989-07-11
Also published as: IT8619590A0; SE8601349D0; BE904483A; FR2579198B1; AU5487886A; IT1191670B; IN166252B; DE3606217A1; GB2172883A; CH670444A5; FR2579198A1; CN86102711A; SE8601349L; ES8706192A1; GB2172883B; GB8606912D0; ES553381A0; AU577453B2; JPS61222920A; NL8600740A

Abstract

FLOCCED MINERAL MATERIALS AND WATER-RESISTANT
ARTICLES MATERIALS MADE THEREFROM

Abstract Disclosed are flocced mineral materials which may be utilized to prepare high temperature resistant, water resistant articles. These materials are prepared by utilizing, as a starting material, a gellable layered swelled silicate that has an average charge per structural unit that ranges from about -.4 to -1 and which contains interstitial cations which promote swelling with a source of at least one species of multiamine derived cations.

Description

~:~57~54 ~ 1 - DDJ-7581 FLOCCED MINERAL MATEE`~IALS AND WATER-RESISTANT
ARTICLES MADE THEREFROM

Backyround of the Invention ...
.

It is known that non-asbestos papers and/or 5 sheets may be produced from water-swellable inorganic .
materials and, in particular, swelled silicate gels.
For example, United States Patent No. 4,239,519 is di~ected to the preparation of synthe~ically derived;
inorganic, crystal-containing gellable, water-swelling sheet silicate~ and certain articles, such as papers, fibers, film~, boards, and coatings, produced therefrom. '''F
These non-asbestos papers and/or sheets exhibit good high temperature stability and good chemical resistance~
Furthermore, sinc~ asbestos fibers are not utilized in~.
their manufacture, such articles will not have the health hazards which are associated.with asbestos contai~ing articles.
U. S0 Patent 4, ~39,519 teaches the method for making the precursor gellable silicates used to produce said papers or sheet articles, as involving three fundamental step~: ~a) a fully or predominantly crystalline body is formed which contains crystals ~onsisting essentially of a lithium and/or sodium water-swelling m~ca selected from the group of fluorhectorite, hydroxyl hectorite, boron flurophlogopite fluorphlogo-pite, hydroxyl boron phlogopite~ and solid solutions between those and o~her structurally compatible species ~:~5~0~4

- 2 - DDJ-7581 selected from the group of talc, fluortalc, polylithio-nite, fluorpolylithionite, phlogopite, and fluorphlogo-pite; (b) that body is contacted with a polar liquid, normally water, to cause swelling and disintegration of S the body accompanied with the formation of a gel; and (c) the solid:liquid ratio of the gel is adjusted to a -L
desired value depending upon the application therefor.
Glass-ceramics are the preferred crystalline starting bodies. Those products are then contacted with a source of large cations, i.e., with an ionic radius larger than that of ~he lithium cation, to cause macro flocculation of the gel and an ion exchange reaction to take place between the large cations and the Li+ and/or Na~ ions from the interlayer of the crystals. .. -Alternatively, U. S. Patents No. 3,325,340 and ...

3,454,917 teach producing aqueous dispersions of vermiculite flaked crystals which have been caused to swell due to the introduction therein of interstitial ions such as ~1) alkylammonium cations having between 3 and 6 carbon atoms inclusive in each carbon group such as methylbutylammonium, n-butylammonium, propylammonium :
and iso-amylammonium, (2) the cationic form of amino- -acids, such as lysine and ornithine, and/or (3) lithium. .. ~.
While the articles, such as papers, sheets 25 and films, prepared via the prior art processes set forth above exhibit excellent heat resistance and are useful in a wide variety of applications, it has b~en discovered that such articles generally do not exhibit good sealing characteristics, thus curtailing their use t 30 as gasket materials. The prior art articles also exhibit a certain amount of water sensitivity which is generally exhibited by the articles having a considerable loss of strength and general deterioration of mechanical and electrical properties when exposed to 35 high humidity environments or submerged in water or other polar liquids. This sensitivity to water correspondingly limits the utility of these articles in certain applications, such as, for example, head ~2 57 ~ ~
_ 3 _ DDJ-7581 ~ske~r ~l~ctr~Leal ~nsulators, environmental protective coa~1ngs, ~nd w2lshable ~nd environmerltally stable building m~S:eri~

Fire-resistant, non-asbestos articles can be mac.e from a swelled,:layer~d flocced silicate gel material that is prepared by u~ iæ~ng ~n exchang4 cation ~hat is ~electe~ from guanidin~ deriv~ti~es~ Such articles were 10 ~urpr~ ly ~hown to exhibit more water resistance than articles prepar~d via prior ~t pr~cesses and have excel~ent elecerical p~operties.
~ntion It ha~ now been unexpectedly discovered that 15 high temperatur~, ~ire-resistant, non-asbestos, water-reslstant articles, ~uch as s)~eet, paper, board, film, f~ber ~nd coating ~rt~cle~, c~n be made from a swelled, l~yered flocced ~ilicate gel ~terial tb~t is prepared by utlli2~ng ~ exchange cation that ls selected rom mult~amine deri~t~ve~. Such 8rticles 5urprisingly have been ~ound to exhibit, ~n general, ~uch improved results in ten~le ~trength and puncture Ees~ stant tests that are conducted when the ~rticles are we~ than do ~aterial~ that ~re prepared utilizing prior art exchange cation3. Further~ore, the articles made according to the pr~sent lnventlon gene~ally display superior ~lectrical ~nd mechanical propertie~ o~er those materials ~ade by pr~or ~r~ m~thods.
Wit~ ~efe~ence ~o heat resistance, ~e article~ that are produced according ~o the present inYent~on ~re co~pletely ~table ~o temperatures o~
zpprox~ma~ely 350-400C ~nd ma~ntain their structural stability to approxi~ately 80DC~
~etai~ed DescriPtion of the Invention ~h~ ~rt~cles snd the ~locced mineral ~uspen~ons o the pres~nt in~ention are, in one embodi-~ent o~ the ~nven~ion, prepared by u~ilizingr ~s a ~ta~ing ~terial, ~ w~ter-s~e~li~ sheet silicate that ~ZS7~5~

- 4 - DDJ-7581 has an average charge per structural unit of from about -.4 to about -1 and which contains interstitial exchangeable cations that promote swelling~ The speeifie exchange cations in the starting material will depend on the silicate being utilized. For example, if a synthetieally derived gellable silicate, which is made aceording to the procedures of U. S. Patent 4,239,519, is utilized as a starting material, the exchange cations will generally be Li+ and/or Na+ ions. If a natural vermiculite dispersion, such as made according to U~ S.
Patent 3,325,340, is utilized, the exchange cations will generally inelude alkylammonium cations and the other eations speeified in U. S. Patent 3,325,340. The silicate, whether synthetic or natural in origin, will most often have morphologies that are represented by thin flakes whieh are generally dise, strip, and/or ribbons.
Although I do not wlsh to be limited to any specifie measurements for the flakes, they will typically have measurements whieh are from about 500 A to 100,000 A, and preferably 5,000 A to 100,000 A in length, 500 A to 100,000 A in width, and less than 100 A thick.
The term "eharge per structural unit" as used in the speeifieation and elaims refers to an average eharge density as speeified by G. Lagaly and A. Weiss, ~Determination of Layer Charge in Mica Type Layer Silieates,~ Proceedings of International Clay Conferenee, 61-80 ~1969) and G. Lagaly, ~Characterization of Clays by Organic Compounds,l' Clay Minerals, 16, 1-21 (1981).
The starting silieate ean be made according to the afore-mentioned procedures of U. S. Patent 4,239,519; 3,3250340i or 3,434,917 or other methods which result in dissoeiated layer materials with charge densities in the desired ranges.
The silieate is then contacted with a source of at least one species of multiamine derived cations to thereby effect an ion exchange reaetion to occur between the cations and the interstitial ions. This ion ~.2~i~054 _ 5 _ DDJ-7581 exchange reaction may be carried out between the cations and the silicate material to thereby form a floc which is then utilized to form the articles o~ the present invention. In another embodiment of this invention, the starting silicate can be directly formed into a product, such as a lithium fluorhectorite fiber or film by using the procedures of U. S. Patent 4,239,519, and a cationic exchange reaction utilizing the multiamine derived cations can be ca~ried out with ~he product, such as by immersing Sh~ product into a solution of multiamine derived cations. Thus, the ion exchange reaction may be carried out in situ during the actual forming process for the product. -The term ~multiamine derived cations", when used in refe~ence to the exchange cations that may be utilized in the present invention, refers to low molecular weightt non-polymeric, di, tri and/or tetra amino functional compounds, wherein the amine moieties have been modified, such as by being protonated, to thereby be positively charged. Diamines are the multiamine compounds of choice. The preferred diamines will generally correspond to the Formula R3N - tCX2)n - NR3 wherein (1) each R is independently selected from hydrogen, a Cl-C8 straight or ~ranched chain alkyl group, a C3-C6 ayclic alkyl group, or an aryl group, with the proviso that there be no more than one aryl group on each nitrogen, t2) each X
is independently selected from l-ydrogen, an alkyl group or an aryl group and (3) n represents an integer from 2 to 15, with the option that, when n is 3 or more, the CX2 groups may form ringed moieties which may be aromatic.
The flocced mineral suspensions of the present invention are prepared, for example, by reacting, generally with agitation, a sui~able silicate gel with a source of exchange cations derived from suitable multiamine compounds in order to effect an ion exchange between the multiamine derived cations and the .

~LZ5705a, interstitial cations in the silicate gel to form exchanged macro 1Occulated particles.
As stated above, one or more exchange cations can be utilized in the cationic exchange reaction.
S Since the various cations will give floc, and eventually articles~ with differing physical properties, the specific cation or combination of cations will be chosen by the practitioner of this invention based on the desired end use.
~he terms ~multiamine derived cations" or "cationic derivative" or the like is used in the specification and claims to indicate that the center for cationic activity is centered on the nitrogen groups in the multiamines. Generally, this is accomplished by protonating the multiamines to thereby form ammonium groups which are positively charged. This protonation has to take place before the cationic exchange can be made with the swelled silicate gel.
The flocced mineral suspension may be used to 20 form the desired articles. The specific treatment steps -applied to the floc will depend on the particular article being formed. For example, if the articles of the present invention are to be formed into sheet materials, the resultant exchanged floc will be agitated with sufficient shear to produce a particle size distribution which leads to suitable particle packing in the sheet forming operation. Following this process the floc is optionally washed to remove any excess salt solution and the consistency of the flocced slurry is adjusted to ~rom about 0.7S% to about 2% solids. To promote better drainage rates on a fourdrinier wire, polyelectrolyte flocculating agents can then be added to the slurry at a level of from about 0.1% to about 1~, and preferably 0.2%-0.3% of floc solids. One example of a suitable polyelectrolyte flocculating agent is Polymin P, which is a trademark of BASF Corporation for a polyethylene imine.
T~is slurry is then.fed to a papermaking ~2~;70~;4 :

apparatus where it is dewatered by free drainage and/or vacuum drainage followed by pressing and drying on drum driers. The thu formed sheet material can be used in applications such as gaskets and the like.
Xf desired, and depending on the intended end use of the articles, additional inert materials may be added to th~ flocced mineral suspension. For example~
if desired one or more fibrous materials from the group of natural or synthetic organic fibers or inorganic fibers may be added to the floc to improve its drainage rate and to provide an end product that has improved strength and/or handleability. For example, when the desired end products are gaskets, the fibers of choice ;
are cellulose fibers, glass fibers, and/or Kevlar fibers (Kevlar is a trademark of DuPont Corporation for an aromatic polyamide fiber). In addition, synthetic latex or other binders may be added to the floc to provide for a product with improved strength characteristics.
Alternatively, the cationic exchange reaction can be conducted directly on a product formed from the silicate starting material. In this ca~e, any desired additional inert materials would be added to the slurry containing the silicate starting material prior to the ~ormation of the product and, of course, the subsequent ;~
cationic exchange reaction.
It has been discovered that epoxy resins are particularly useful additives to articles formed according to the present invention. The use of such resins adds strength to the final product and, when used 30 i~ conjunction with diamine exchanged floc, seem to i~
promote a dual functionality in the diamines, which act, not only as exchange cations for the sheet silicate material but also as a crosslinking agent for the epoxy resins. The resultant product has enhanced strength, chemical resistance and dielectric properties.
The term ~water resistant" as used in the specification and claims is not meant to imply that the articles of the present invention are waterproof or are ~257~5a~

completely impervious to water. By contrast, the term is used to indicate that the materials do not substan-tially degrade, at least in their tensile strength and puncture resistant properties/ when exposed to water.
In addition to being water resistant and having excellent fire and heat resistant, it has ~een discovered that the articles of the present invention possess excellent electrical properties and are thereby suitable for a variety of applications, including electrical insulators, cable wrap and, in particular, printed wiring boards.
In these following Examples, unless otherwise specified, the starting material utilized was a lithium fluorhectorite made according to procedures taught in U. S. Patent No. 4,239,519.
Example 1 ~his example illustrates a method of producing both a diamine exchanged fluorhectorite flocced silicate and a formed shee~ that was prepared therefrom.
A slurry o 1,6 hexanediammonium fluorhec-torite (made from the corresponding diamine) was ;~-prepared by adding 200 grams of a 10~ dispersion of lithium fluorhectorite to 2 liter~ of lN 1,6 hexane~
diamine HCl solution. The slurry was then agitated with a high shear mixer to reduce the particle size of the resultant floc, was washed and then was analyzed for water content and diluted to result in a 2% solids slu~ry. The slurry was transferred to a 11.5" x 11.5"
hand sheet mold (manufactured by Williams Apparatus Co.~ ;
and dewatered. The resultant formed sheet was then wet pressed and dried on a drum drier.
The sheet had good flexibility and performed well in the gasket sealing test.
Example 2 3S Using the procedures of Example 1, a handsheet was prepared from the following slurry:

~2S7054 _ g _ DDJ-7581 Wt. Percent Hexamethylene diammonium fluorhectorite 58.7 NBR latex 3.2 Alum 2.9 Micro Talc 5.9 Redwood Fiber 20 9 `
Kevlar~ Fiber 2.9 Mineral Wool 23.5 Total 99O2 ~he resulting handsheet was subjected to .
gasket sealing tests which were electro-mechanical air lea~age tests conducted according to the specifics set forth in pages 1-3 of the SAE (Society o~ Automotive ,:.-Engineers, Inc.) technical paper No. 83022 (ISS~
0148-7191 (83/0228-0220, 1983).
The results of the tests were: .~.
Initial Flange P~essure (psi) Leakage Rate - :
(psi/min) :~
570 1.389 20 915 1.587 2500 0.529 !:
Example 3 This example illustrates a method of producing films of the present invention wherein the cationic .~s 25 exchange is made in situ. ~.
A 10% ~olids lithium fluorhectorite gelled dispersion was prepared according to proeedures taught in U~ S. Patent No~ 4~239,519. A film was made of this material by using a 4.5 mil Byrd applicator, which was 5 i~
30 inches wide, to draw down a 4~ mil thick wet film of the !
dispersion on a glass plate. The glass plate, with the film attached, was then immersed in a 0.25M solution of 1,6 hexanediamine HCl solution to cause a cation exchange between the 1,6 hexanediammonium cations and the fluorhectorite's interlayer cations. A skin was formed, seemingly instantaneouslyt on the film which indicated such an exchange was taking place. In 10 minutes the film was removed.from the plate, washed in ' .
.

~s~s~

deionized water to remove residual salts, and dried.
The film had good flexibility and strength retention when wet. - --Exam~les 4-15 For each of these examples, the procedure of Exampl~ 3 was substantially repeated with the exchange cation (all made from the corresponding diamine~ as specified to form the corresponding film.

Example Exchange Cation 4 N,N,N',N-tetramethylethylenediammonium O-phenylenediammonium S 1,2 diammonium propane 7 lt8 diammonium octane 8 2,5 toluenediammonium lS 9 1,7 diammoniumheptane 1,9 diammoniumnonane 11 1,5 diammoniumpentane 12 1,2 ethylenediammonium 13 1,3 diammonium propane 20 14 1,4 diammonium butane 1,12 diammoniumdodecane Comparative Examples 1~3 These comparative examples illustrate fluorhec-torite films that are made with various prior art exchange cations. Four and one half mil thick films o potassium fluorhectorite (XFH) and ammonium fluorhectorie ~N~4FH) were separately prepared by the process specified in UO SO Patent Wo. 4,239,519. A
film was then cast of both the KFH and a NH4FH slurry.
A Kymene (a trademark of Hercules, Inc. for a cationic, polyamide-epichlorohydrin resin) fluorhectorite film was also prepared by the procedure of Example 2, except that (1) a 3.0% Kymene solution was used and ~2) the lithium fluorhectorite film had to be immersed in the Kymene solution for 2 hours until the resultant exchanged film was sufficien~ly self-supporting to be ~Z57054 removed from the glass plate. These films, along with the f ilms made in Examples 2-9, were then subjected to tensile strength and puncture resistance tests which were conducted as follows:
Tensile Stren~th Measurements Dry tensile strength measurements were determined using an Instron at 1~" jaw separation and 0.2n/min. crosshead speed. Wet strength measurements were made ~y bringing water-saturated sponges in contact with both sides of the film sample for 10 seconds ~Jhile the sample was positioned in the Instron clamps just before the strength test was conducted.
Puncture Resistance Measurements A sample of film was secured in a retaining ; -device which held the film securely. A stylus which could be loaded was impinged on the film in the .
direction normal to the surface of the film and loaded with increasing weight until the stylus penetrated the film. In the wet test the film in the retaining device was submerged in deionized water for 10 seconds immediately proceeding the puncture resistance test.
The data from these tes~s is shown in ~he ~:
table below.
TABLE
Tensile Puncture Film of Strength Resistance Example Exchange ~psi) (gr/mm) # _ Cation ~y Wet ~ Wet 3 1,6 hexanediammonium 1600017000 13000 ~000 3 0 4 N~N~N ~ ,N te'cramethyl-ethylenediammonium 1800016000 11000 5100 O-pehnylenediamine 1300015000 7600 3000 6 1,2 diammonium propane 13000 11000 14000 4200 7 1,8 diammoniumoctane 12000 11000 6500 1700 8 2,5 toluenediammonium 9800 11000 6500 1800 9 1,7 diammoniumheptane 7300 8800 16000 7500 1,9 diammoniumnonane 70005000 3600 1400 ~25705~ -11 1,5 dia~moniumpentane 6600440005700 5200 12 1,2 ethylenediammonium 520036001200 600 13 1,3 diammonium propane 330014003500 680 14 1,4 diammonium butane 300014006600 900 15 1,12 diammoniumdodecane 1800 2900 3100 570 ,. ..
Comparative Example #
1 Kymene (protonated) 7,0002,700900 260 2 Ammonium 3,3001,4003,500 680 3 Potassium 1,1002003,300 440 The data indicates that the films made accor- ;.
ding to the procedures of the present invention have markedly superior wet tensile strength and/or superior wet puncture resistance when compared to prior art compositions.
Fire and Smoke Resistance A film prepared according to Example 3 was, -:
after being dried, subject to fire and smoke resistant test~ in accordance to the procedures speci~ied in . :
ASTM-E-662-79. Three separate tests were made and the results are set forth below.
Test 1 - Flameability (The numerical values correspond to the maximum specified optical density as per N.B.S.
Technical Note ~708.) Flaming Mode O
Smoldering Mode O
Test 2 Oxygen Index Type C ASTM D2863-77 Critical Oxygen Index 100~ 2 Test 3 Radiant Panel AST~E162 79 Flame Spread Factor 1.00 Heat Evolution 0.0 Flame Spread Index 0.0 ~2S70~

Electrical Pro~erties A film of Example 2 was, when dried, tested for dielectric constant and dissipation factors using the procedures of ASTM D150 and for dielectric strength using the procedures of ASTM D149. The results, set forth below, indicate the ilm has utility in a variety of elec~rical insulating properties.
Dielectric Dissipation Constant Factor 100 HZ at 25C 26.53 .288 100 HZ at 300~C 3~.9 .37 100 HZ return to 25C 10.7 .049 100 RHZ at 25C 12.19 .153 :
100 KBZ at 300C 15.0 .202 100 KHZ return to 25C 9.52 .024 Dielectric strength measured at 577v/mil.
Com~arative Examples 4 and 5 These examples illustrate using, as a starting material, silicate materials which fall outside the scope of the present invention in their charge per structural unit and their physical measurements.
For comparative Example 4, a 10% aqueous dispersion was made from a natural hectorite obtained from the source clay minerals depository of the Clay ---Minerals Society, Bloomington, Indiana. For Comparative Example 5, a 10% aqueous dispersion utilizing sodium montmorillonite, which was obtained from the same so~rce. In each example, a film was drawn down using the procedures set forth in Example 2. The glass plates were then immersed for 10 minutes in a 0.25 M 1,6 diammonium hexane solution~ In both instances, a coherent film was not produced.
Exam~le 16 Thi~ example illustrates a method of preparing a film of ~he present invention utilizing a vermiculite starting material:
A 10% solids suspension of n butylammonium vermiculite, whlch was prepa~ed according to the ~L~57(~54 -- 14 -- DDJ-75~1 procedu~es specified in U. S. Patent 3,325,340, was cast as a film on a glass plate according to the procedure set forth in Example 2. The glass plate, with the film a~tached, was immersed for 10 minutes in a 0.25 M
l,S hexanediamine HCl solution. The resulting fil~ was removed from the plate, washed, and dried. The film displayed wet strength in the tensile strength and puncture res;stance tests that a comparable unexchanged vermiculite film does not display.
~
This example illustrates preparing fibers utilizing the method of the invention. A 15% solids suspension of lithium fluorhectorite (prepared as above) was extruded through an 11 mi~ opening needle into a 2N ~' lS solution of 1,6 hexanediamine HCl. The extruded fiber was carried by a porous belt and delivered to a second bath of 2N 1,6 hexanediamine HCl. The fiber so produced was washed via submersion in deionized water and dried.
The re~ultant fiber was strong and flexible.
Example 18 This example illustrates the addition of an epoxy to sheet silicate composites.
Codispersions of the diglycidyl ether of bisphenol A (DG~A~ and lithium fluorhectorite ~LiFH) were prepared by adding the epoxy to a 10% (solids) aqueous lithium fluorhectorite dispersion. The codispe~sion was then mixed via a high shear processO
The codispersions were formed in the following ratios of LiFH to DGBA:
1. 100 gr. 10% solids LiFH dispersion (10 gr.
LiFH solids) 0.1 gr. epoxy tapprox. 1% on solids basis).
2. 100 gr. 10% solids LiFH dispersion 1.1 gr.
epoxy (approx. 11~).
3. 100 gr. 10% solids 2.5 gr. epoxy (approx.
25~).
The films were prepared by producing 4.5 mil wet films on glass plates with a Byrd applicator and immersing the film in a 0.25M hexamethylene diamine HCl ~25705a~

soln. at a pH of 7Ø The resultant films had good wet strength characteristic of hexamethylene diammonium exchanged fluorhectorite. The resultant film was washed with deionized water to remove excess hexamethylene

5 diamine HCI and dried at 60C. The dry films which were flexible were heated to 150C for 3 hours. rrhe resultant films exhibited increased rigidity as would be expected with epoxy curing. Therefore, it appears that the hexamethylene-diammonium cation is effective in performing the layered silicate exchange function and epoxy curing.
For an alternative method of making the articles, epo%y/fluorhectorite codispersions as described above were converted to floc form through the addition of the codispersion to a 0~25M
hexamethylenediamine HCl solution with agitation. After washing the excess hexamethylenediamine HCl from the floc the 10c solids content was adjusted to 2% and subjected to high shear mixing to reduce the particle size. The resultant material was transferred to a nonporous mold and allowed to dry to coherent flexible films of approximately 10 mils thickness.
The films were hot pressed at 150C for 3 hours and the films become more rigid.
From 1 to 80 weight parts of epoxy resins can be utilized in producing articles according to the present invention~ based on the solids weight of the sheet silicate starting material.

Claims

WHAT IS CLAIMED IS:

1. A method of preparing a flocced mineral material that can be utilized to form a non-asbestos high temperature article that exhibits water resistance, which method comprises contacting a swelled layered silicate gel that has an average charge per structural unit that ranges from about -.4 to about -1 and which contains exchangeable interstitial ions with at least one species of multiamine derived cations to thereby effect an ion exchange reaction between at least some of the exchangeable interstitial ions and at least some of the multiamine derived cations.

2. The method of claim 1 wherein the multiamine derived cations are diamine derived cations.

3. The method of claim 2 wherein the gelled layered silicate is a synthetic gellable silicate and the interstitial ions are Li+ and/or Na+.

4. The method of claim 3 wherein said synthetic silicate is prepared by contacting a body consisting essentially of crystals of a water-swelling mica selected from the group of fluorhectorite, hydroxyl hectorite, boron fluorphlogopite, hydroxyl boron phlogopite, and solid solutions among those and between those and other structurally compatible species selected from the group of talc, fluortalc, polylithionite, fluorpolylithionite, phlogopite and fluorphlogopite, with a polar liquid for a time sufficient to cause swelling of the crystals accompanied with the formation of a gel.

5. The method of claim 4 wherein the crystals are fluorhectorite.

6. The method of claim 5 wherein the diamine derived cations are selected from the group of 1,6 hexanediamine, N,N,N',-tetramethylethylenediamine, O-phenyldiamine, 1,2 diaminepropane, diamineoctane, and 2,5 toluenediamine.

7. The method of claim 3 wherein the polar liquid is water.

8. The method of claim 2 wherein the silicate is vermiculite and the interstitial ions are alkylammo-nium cations, the cationic form of amino-acids and/or Li+.

9. A flocced mineral material which comprises a swelled layer silicate gel that has an average charge per structural unit that ranges from about -.4 to about -1, said silicate containing at least some interstitial cations that are multiamine derivates.

10. The material of claim 9 wherein the multiamine derivatives are diamine derivatives.

11. The material of claim 10 wherein the silicate is synthetically derived.

12. The material of claim 11 wherein said silicate is prepared by (1) contacting a body consisting essentially of crystals of water-swelling mica containing interstitial lithium and/or sodium cations, said mica selected from the group of fluorhectorite hydroxyl hectorite, boron fluorphlogopite, hydroxyl boron phlogopite, and solid solutions among those and between those and other structurally compatible species selected from the group of talc, fluortalc, polylithio-nite, fluorpolylithionite, phlogopite and fluorphlogo-pite, with a polar liquid for a time sufficient to cause swelling of the crystals accompanied with the formation of a gel, and (2) contacting the thus formed gel with at least one species of a cationic diamine derivative to thereby effect an ion exchange reaction between at least some of the lithium and/or sodium cations and at least some of the diamine derived cations.

13. The material of claim 12 wherein the crystals are fluorhectorite.

14. The material of claim 12 wherein the polar liquid is water.

15. The material of claim 12 wherein the diamine derived cations are selected from the group of 1,6 hexanediamine, N,N,N',-tetramethylethylenediamine, O-phenyldiamine, 1,2 diamine propane, diamine octane, and 2,5 toluenediamine.

16. The material of claim 10 wherein the silicate is vermiculite.

17. A high temperature, water resistant article with good electrical properties that comprises a swelled layered silicate that has an average charge per structural unit that ranges from about .4 to about -1, said silicate containing at least some interstitial cations that are diamine derivates.

18. The article of claim 17 further comprising an epoxy resin.

19. The article of claim 17 which further is a sheet material.

20. The article of claim 17 which further is a fiber.

21. The article of claim 17 which further is a film.

22. A method of preparing a high temperature silicate article that exhibits water resistance and good electrical properties, which method comprises contacting an article formed from gellable layered water-swelling silicate that has a charge per structural unit that ranges from about -.4 to -1 and which contains exchangeable interstitial ions with a source of at least one species of multiamine derived cations to thereby effect an ion exchange reaction between at least some of the multiamine derived cations and at least some of the interstitial ions.

23. The method of claim 22 wherein the multiamine derived cations are diamine derived cations.