DE1929712A1 - Binders and gels based on colloidal silica - Google Patents

Description

E ₄ I. You POIiO? DE HEMOUES JUTO COMMIT 10tii and Market Streets, Wilmington, Delaware 19 898, V _o 8t

Binders of gels on the basia of colloidal silica

The invention relates to binders based on colloidal silicic acid, formed from these binders Products and processes for the manufacture of such binders and molded products.

A very large number of different silica-based binders are already known. For example, it is known to use alkaline ionic silicates such as sodium metasilicate, tetramethylaiamonium silicate and tetraethanolaionium silicate. These binders are generally successful for binding grains of sand to roofing felt and as binders Used in zinc-rich paints. When air-dried or by heating, strong, rigid bonds are formed. These alkaline ionogenic silicates, however, are water-sensitive and, given their low soaking and softening points, of limited use high temperatures.

001011/12711

Alkaline ionic silicates neutralized with aqueous or gaseous acidic substances have proven to be valuable for binding catalysts and for the production of heat-resistant putties. However, these polymerized silicates cannot be produced with a high content of pesticides because gel formation occurs almost immediately during neutralization; It is therefore impossible to obtain homogeneous substances by mixing concentrated solutions of acids and of alkaline ionogenic silicates. If gels are made by mixing dilute solutions of acid and silicate, they will shrink and crack on drying. Furthermore, the large amounts of neutral folds that they form during neutralization, if they are not washed out, affect the heat resistance of the gels and theirs Value as a binder for catalysts «As a result of the extremely fine-pored structure of these gels, in which the pores rarely exceed 100 % in size, it is often impossible to completely remove these salts from thick-walled molded bodies =,

Men can use reasonably concentrated solutions of silicic acid esters, as hydrolysiertom orthosilicic acid ethyl ester, heral'sllen and these solutions by adjusting the pH values in for The practice is never too long and not too short a time to develop brin ^ ea, Such binders are admittedly advantageous for Production of νο, ι molds for: the precision mold casting and of foru capsules used for casting polished metals; the Silicic acid residues are quite expensive each, and the alcohol, the inevitably forms when using ethyl orthosilicic acid, carries the risk of fire, explosions, and sanitary damage.

N aqueous .'colloidal amorphous silica sols are as heat bf? a permanent binders and for dividing molds for dan Precision foruiiues have been discarded. The flocculation odor Coagulation of the colloidal silica particles for the purpose of gel formation from these sols is carried out by adjusting the pH of the sol

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adjusted to a range in which the particles have a low charge, and at the same time a neutral salt, such as magnesium chloride, is added to help the destabilization. Such gels have a number of advantages over the gels obtained by neutralizing alkaline ionic silicates: their mean pore diameter is large and their contamination by salts can be kept at a lower level Limit value. First, they have long solidification times from, for example, 15 minutes to many hours. Second, these gels are relatively weak because the colloidal particles are only bound to one another on their surfaces and only there at the points of contact. The larger the colloidal parts, the smaller the number of atoms that are on the surface of the particles, and the smaller the number and strength of the bond points in the structure of the violin. Therefore fine colloidal particles can indeed verhältniamäecig 5-30! Diameter but especially the smallest, gerniassen well to each other by these particles binden§ Z ^ e Bindefeatigkeit between diving with Great above i> u πιμ is so low, the gels virtually no Dao Have abrasion resistance. In fact, gels that consist of particles with diameters greater than about? 0 πιμ disintegrate on drying; As a result of the drying process, the parts often merge into a dense, hexagonal or orthorhombic packing.

Iil the Erkennti.is these shortcomings of Kieselsäurosole as gel-BIZI finer mar has tried the verhältuismäBsig weak Bindur. £ share it ir to by flocculation or coagulation of Kieseleäureaolen gels produced verstärkenο The US Patent 2 765 24-2 describes-a Verstärkungaverfahren In which the gel is obtained, migrate material from the points of the strongest curve to the points with a negative radius of curvature at the points of contact between the particles

009811/1270 ORIGINAL BATHROOM

can also be reinforced by adding colloidal silica with a high specific surface area. Although one achieves considerable increases in gel strength in this way, these methods cannot generally be applied to the production of macroscopic shaped bodies, since the reinforcement only occurs after the gel has formed However, a large amount of water is not practical because it takes an extraordinarily long time and a homogeneous distribution of the reinforcement cannot be achieved. The method of heating is suitable to bring about the reinforcement of large gel masses, which consist of small parts of colloidal silica, but if the gel parts have a diameter of more than about 30 ταμ , one hardly achieves any significant reinforcement in this way.

There is therefore a need for fast-gelling binders based on silicic acid with a high solids content, which in Gels of good heat resistance, high strength, abrasion resistance and porosity, large pore diameter and regular pore size distribution pass over. The invention lies the task is to make such binders available.

The subject of the invention is a mass which is characterized by the fact that it

(a) EU 0 to 9 * 5 percent by weight of a particulate or fibrous; on JWllstoff and

(b) about 5 ms 1 '; ea colloidal amorphous silica middle 0 weight percent of an aqueous binder support admits in turn 20 to 75 with a Gewichtsprozcni Te inside diameter from 5 to 500 ημ., X to Y mol of dissolved alkaline ionic silicate per 1000 g of carrier from the silicon dioxide, where X and Y are represented by the equations

009111/1270 BAD

X = 10 Y * 10

1.90-1 (1,762 + 21 * 2 Mf +

3.70- | (1 · 762

"are determined in which 0 is the volumetric proportion of the Silica in the carrier, D is the mean particle diameter and S is the number of moles of dissolved cations excluding hydrogen ions per 1000 g of carrier of silicon dioxide, with the proviso that X is not less than 0.083 and Y is not greater than 1.67, and contains such an amount of acid that the pH of the carrier is in the range from 5.0 "to 9.5«,

The invention also relates to a silica gel which is from 0 to 95 percent by weight of a particulate or fibrous Filler and at least 5% by weight of amorphous colloidal silica particles with a medium Teilchandurehraesser from 5 to 500 πιμ consists, with the colloidal Silica particles by 0.5 to 10 percent by weight polymerizes ^ alkaline ionogenic silicate in the form of a porous, three-dimensional network are rigidly connected to each other.

Furthermore, the invention relates to a silica gel which consists of 0 to 95 percent by weight of a particulate or fibrous filler and at least 5 percent by weight of amorphous colloidal silicon dioxide particles with an average particle size of 5 to 500 ΐημ, the diameter of essentially all colloidal ones Silicon dioxide particles are 0.8 to 1.2 times the mean diameter, the colloidal silicon dioxide particles are rigidly connected to one another by 0.5 to percent by weight polymerized an alkaline ionic silicate in the form of a porous, three-dimensional network, the diameter}? of at least 60 i » the Po-

00901t / 1270

BATH Q

ren in DEM network, the 0.8 to 1.2 of the average faohe Porendurohmessers amount, the average? orendurchmeeaer is 0.5 to 1.5 times the average Seilohendurooaessere, the pore volume of the network 45 to 75 $ of the Hetsvolumens and the transverse breaking strength of the gel is at least 105 kg / om.

Furthermore, the invention relates to a method for the production of shaped products, which is characterized in that that he (1) deforms a mass that

(a) from 0 to 95 percent by weight of a particulate or fibrous filler and

(b) consists of 5 to 100 percent by weight of an aqueous binder carrier which in turn contains 20 to 75 percent by weight of colloidal amorphous silicon dioxide an average particle diameter of 5 to 500 πιμ, X to Y moles of dissolved alkaline ionic silicate per 1000 g of carrier excluding the silicon dioxide, where X and Y are represented by the equations

90-§ (1,762 X - 10 ^J

[1.70-Jk 1.762 + 2JiS) Jf ₊ | Y 3 10 * - - '

where 0 is the volumetric fraction of the silicon dioxide in the carrier, S is the mean particle diameter and S is the number of moles of dissolved cations with the exception of hydrogen ions per 1000 g of carrier excluding silicon dioxide, with the addition that X is not less than 0.083 and Y is not greater than 1.67 and contains such an amount of acid that the pH of the carrier is in the range from 5.0 to 9.5, and

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BAO OR (GfNAL

(2) the Maeae for a period of time sufficient for gel formation from 5 to 300 seconds in the desired shape.

The invention is based on the finding »that the in © inen Aquasol extract the colloidal silicon dioxide already present as they are in the sol, immobile in place can be made or "frozen" by adding a small, controlled amount of water-soluble alkaline ionogenas 3ilioat adds and controls the process conditions so that a polymerization of the ionic silicate is preferred the silica particles already present takes place without the silica particles coagulating or flocculating will. In order to achieve this desired result it is essential that a number of variables be taken into account be, nömlioh the concentration and Teilohengrösoe dor colloidal amorphous silica particles, the pH of the Solutions and the amount of neutral salts present. Besides The following description shows that these verjatlcn: *. ii their effects are interdependent and therefore r '.: j - DeZiehung < must be taken into account with each other.

The binder carriers according to the invention differ from the known, colloidal silica-containing binary carriers in several respects. The carriers "euäae d: jr invention contain a carefully controlled, relatively small amount of a water-soluble alkaline but ior-ogeiiiii -: i licat in." Combination with concentrated sols of b: ij? -3ite i'c · 1; 1-gen amorphous \) .liciumdioxiate particles. The mer-ge and j? 3: 51chei .rösac of the colloid, len silicon dioxide, the cons "ent ^.: - tio: i and heig: des allcaliechtu ionogenic silicates, the sc '"z'& an /.- intv ation _t These components are carefully related to each other and the pH value is carefully matched to one another, so that you can peel, peel, peel and hold a chill of a 5 b:> ε 300 seconds, X "er - aeemte silicon dioxide content is much higher than that which in the end does not contain ionic alkali alloys

00 ti 11/1270

* ^m

or can be achieved with orthosilicic acid ethyl ester solutions can, and the gels according to the invention therefore result in a great deal smaller dimensions to the difficulties of shrinking and Jumping than the known gels. Compared with binder carriers, which only contain colloidal amorphous silica? arstare the wearers of the invention achieve much faster, have controllable solidification times that are suitable for most applications application purposes are within an advantageous range, and have a much firmer violin structure. The carriers according to the invention are also cheaper than, for example, orthosilicic acid ethyX-'esters and can be produced by simply mixing raw materials with a good shelf life.

Me free geiaäo 3 of the invention have ... a unique combination of "preliminary" properties, namely an unusual degree of strength and abrasion resistance, high porosity and exceptionally large pore size!. \? R. If men silica sol ') with a narrow leilchengröBeenvertöilung, the gels obtained also show one very regelmässigG Porcngrössenverteilunge The Fo of the gels gemäsi' of the invention biatet very happy if the gels .Is catalyst support used for separation processes or for purposes \ -;? Nva ^ n _f at done> i aa auf Hitzebf> e-if '.. diglreit ankoninto' vena die Poran ir a *, α R ^; 5rpe: e from i ^c jili ': - j, vjraii x; d heteroger sinl u? ii a receipt: 'oh ~' oa IrI saw a se l \ ez \. bc-Ivl · ßroeseii pores a \ ifwe I, ';<; ■ - · _t ' / ei ^1. * ii;?: ·: -., -l & n Ter- ) felri-a c> .a Sir. sv-ns oä-jr der V8r :: 'ostigun, v üt' - ^? .- jsi. ^ t ^ uktur, wern old. crhii: Ό wi ?. ¹ = !, also hetiiro ^ an- ^: '». ^: .a } r \ c - '. r: .t-: i Poreu n-3ät; ^: i deua, ε-'ht-n bti right niecirigsn iPer ^ e -Λ: ran zv. s. '. i-vJrL and au? ctiL- Ce.-gef. '^ ö zv. verao: iw: .ndi3n, uriu 15 ". <". (* \ -j ^ A '' · ί? .- 3ζ Wäru strong Käv; äe, <■ \ z 5-5: i'cJtoran S .ntorn ux . r. "irVThprfciX Ti.cl & j · ^ Ιοί- sr 3rd ·. bed _{,. '5} · εης: · χ'" eien i-st -df s>; - ^; esi * ^: 'ij · ■ - dr; · ^! > .. 1 rr-fi ^ o; a

B \ - \; i? Tig. B ': s toi TjVu ". Man we-idf ΐ Ii-i3s.j: .- £"1''iik; - Βλ-.ί-ϊ,'e;;,"■■ - • ix-s. - doors - /: d isTigi! r iiu ^ c-itsn an »j'ie tc ^.: -ώ ^ Γ., η '· -: · ftr ^ inauag, die ε, κ; = SoXen ■ It aiiur en ^ en Ie: lchenäv-b'tapnr-j'teii'-r ^ hc-rg-3-

009811/1270 BAD

is aind, aeigen due to the extraordinary rules their packing does not have this difficulty. Rather, they are characterized by an extremely perfect, open-packed one cubic structure, "in which most of the particles seohs others ! DeiloiisK are surrounded and touch them. Hence tend to ais to their open porosity up to relatively high To maintain temperatures? wenr, but the porosity eliminated practically all of the porosity is accidentally twisted on the same side, and you get exceptionally firm, non-porous images "

Another unusual feature of the gels according to the BrfindtiKg is that their abrasion resistance and their strength are not limited by the size of the silicon dioside particles or the pore size already mentioned, the structure is all the more and \ uu so less abrasion resistant, $ e larger the pore diameter and the partial diameter is "With the gels according to the invention, strength and abrasion resistance can be controlled independently by varying the silicate content so that the gels, the greater Silioiumdioxidteil- included • ihen., as stable, fast and making abrasion resistant laassn as the gels containing small silica All gels according to the invention, Querbruohfestlgkeiten of at least 105 kg / om ² to ₀

In general, it has not outweigh too critical ER, "which of the various available water laudable alkaline ionic silicates * m ± m Eahmen the Erfindiing is recycled. Examples of such silicates are lithium silicate, iatrixuai3iliQat, potassium silioate and the silicates of strong orange bases such as tetramethylammonium hydroxide, tetraafchanolaffilonium hydroxide and guanidine. Alkaline solutions of silicon weaker bases, such as ammonia and organic affinity, are non-ionic and are therefore suitable for the purposes of the invention

Invention suitable, usually have molar ratios of SiO ₂ to alkaline oxide of about 2 to 4i5 »

In other technical respects, it is certain that » Adjustments are made, zJ. the setting dea pH to detect differences in the rate of gel formation Take account of the nature of the cation ionogenic silicates result. Apart from such fluctuations However, the gel formation speed is similar all alkaline ionogenic silicates behave approximately equally for the purposes of the invention.

The concentration of the alkaline ionic silicates - which are the liquid gel thinners, in the binder vehicles of the invention is a borrowed variable. If the amount of the alkaline ionic silicate is too small, the strength of the between the silicone wafers will suffice The bond that forms the polymerisation of the silicate is not formed in order to maintain the almost complete control of the solder present in the solution at the moment of gel formation in relation to the forces exerted by the shrinkage and surface tension of the solvent, if conversely the concentration of the alkaline ionic silica ,; r. is high, many of the difficulties described above occur with regard to the sufficient mixing of a kojicentri-x-tar of silicates with neutralization amittal ; Distance;? hii;.. '3C ei undesirable gro3se Engen of salt, leading to the bmx Schwiarigkei Beinigung and / or leads to the deterioration of the properties or katalyhißenen cer heat resistance.

It was far: * found that too great a slope ac ai.ke:.ischem Silicate formation leads to a heterogeneous structure, in that some parts of the resulting gel give the uterat feirfpori ge structure of a typical bilioate gel known hitherto have, wäli: «end other parts have further, more open-pored parts more frequent structure on weis eii, \ 7ie si? only bol dan ^ aler, according to the end result. Eo vnirde determined that &

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the concentration of the alkaline ionic silica in the Binder carrier according to the invention within the broad Ranges from 0.083 to 1.67 moles, preferably within the Ranges from 0.167 to 1.00 mol, excluding each 1000 g of carrier borrowed the silicon dioxide must be kept.

The concentration of the alkaline ionogenic silicates in the binder solutions according to the invention can be achieved by adding weighed amounts of adjusted solutions of such alkaline ionogenic silicates, or it can be determined analytically by the colorimetric molybdic acid method, which is described in a work on. "The Solubility of Amorphous Silica in Water" by GB, Alexander, WoM. Heston and RK Her in "Journal of Physical Chemistry", Volume 58, 1954, page 453, is described. If the concentration is determined according to the colorimetric molybdic acid method described in this work, the percentage of alkaline ionic silioate according to the invention is that amount of silicate which produces a color in 20 minutes under the conditions prescribed for this analysis »

Many amorphous KieBelaäureeoJ.t are known, which are manufactured according to various processes. Sinige be prepared by "boiapft nan an aqueous solution and is anor- · phο Silioiumd? Ixidteilchen breeds, others are prepared by hydrolysis Oriharieoelaäureäthyleater you and others by oxidation of Üliciumtetrachlorid. Bs aind also ^ ina number of possibilities known, the part cl-enober ^ v.äcLe with *. Kj.eee:, ri. ^: -u;? i-: modify aolen au, z _c B _; the Yerei-t-srv.Eg e'er surface with alcohols and the adsorption of Eehxv. ^r ertJ £ pn. Metal ions »v. Toggle .e aluminum, ice or Chromioi -3n _t at the Teilehenoboi \ r .-: cozy, 'Pur making such ^<c ole has men ready va & lr - "verwandet- ers" h5edene bases as stabilizers; Further? So it is known with the most varied of violet sizes and various degrees of aggregation of the particles

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009811/1270 ORIGINAL BATHROOM

If you want to produce gels with a uniform pore size distribution, you have to start from sols with a fairly homogeneous particle size distribution, since deviations from a uniform particle size distribution are reflected in an expanded pore size distribution of the resulting gel. For the same reason, it is also desirable that the starting sols have as low a degree of existing particle aggregation as possible, if the diameter of all colloidal silica particles in a sol is 0 * 8 to 1.2 times the mean particle diameter then at least 60% of the pora in the resulting gel have a diameter equal to 0.8 to 1.2 times the mean diameter, the mean pore diameter is 0.5 to 1.5 times the mean Particle diameter and pore volume of the gel 45 to 75 $> its total volume _s

The diameter? of the colloidal silicon dioxide particles can vary between 5 and 500 μm and depends roughly on the intended use under consideration. to be used as a catalyst carrier, carrier for chromatographic analysis or in general for purposes in which the binary agent solutions are to be used. According to the invention as the sole component or as the main component tf.es resulting & h1s must be used., is s? sv / sokmägeag? To use particles whose mean diameter has a YiXu minimum value of e; wa 50 ΐημ, because with such applications eire v / ritporigs and gleishiüässiga Sxi-ak ^ / r is zwaokiräsEig, aureh the foreign substances easily into the gel eia + retyi / and can easily emerge from the gel, and veil ec aaö ^ li iü. is, such sole mi. "very high Κ ± β8β \ ΒΒηνβ ^ οιχί. ^ν Λ :: · & - <.: ια-αν _! ι ne-rau ™ put =

V7erm anderserse: 'ta the purpose i >> v Viz.sb ^ t. & iivi, e.g. the invention the ί creation of a ^ itzeboetär ^ Ixgei; BUiüüwL-g'W. a is _P then the pore size is not so important, and oi.na iäienjlieh finely divided structure can then 'aoga; -: · from Yor-tei.I. aairi to be the product: as lower as possible! DempsrE ^ ir- - "att-n- zu tjia.- ήβη.

'.-. ■ la-

009811/1270 BAD ÖRJQINÄL

In those compositions according to the invention in which the binding agent inertia? represents only a small part of the total mass, and the rest of a ceramic material, such as heat-resistant amorphous silica grains, zircon, clay, heat-resistant fibers, such as glass fibers, amorphous silicon dioxide fibers, Aüuminosilatfaser etc., exist, needs the mean diameter of colloidal amorphous silicon dioxide ™ particles to be only 5 ιημ, particles of even smaller It is difficult to use diameter because it is difficult to Mixing ionic silicates with such sols without this To coagulate silica sol

There is a sharp upper limit for the size of the sol particles not. But since particles with diameters of more than 500 ΐημ do not offer any particular advantages, this part size can apply as the upper limit. Particles whose size is above this value tend to settle out of the solution, if « one does not work with short solidification times, and it is therefore difficult to obtain the desired homogeneity of the To maintain structure.

From the above discussion it follows that if one uses too dilute sols of colloidal silica particles, the particles in the binder carriers according to the invention must shrink over large distances as the solvent evaporates in order to achieve the open-packed cubic structure which is used for the gels of the invention is characteristic. Innerhai h certainly) r Grecaen finds such shrinkage tatoäehlich instead: but not l.3t of an undesirably high Ausmasa of 3p-'Ingen or broke the gel structure by the shrinking force "} bagXeitet-. ·

TSs wivrcls? % s £ wi on, d & aa the concentration of the colloidal amorphous Kiesalsävu e in c.8tö Bindeisit ielträger must be kept within the limits of 20 to 75 weight percent. Under a concentration of 20 weight proiseiit, ■ a _e S »eohon bsi a con-

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009811/1270 BAD

aentration of 15 percent by weight, the shrinkage forces are like that big * that the gel cannot withstand them. Such carriers jump very strongly when drying and have practically no value as a binder. With concentrations of colloidal Silicic acid over 75 percent by weight makes the carrier so viscous that that it is difficult, if not impossible, to match him enough to mix with the remaining ingredients of the binder *, to get a homogeneous ε structure. In the preferred binder carriers of the invention, the concentration is of colloidal silica 25 Mb 60 percent by weight.

It is impossible to obtain binders according to the invention or to carry out the process according to the invention by simply adding a certain pH value within the specified range, a certain concentration and particle size of the colloidal amorphous silicon dioxide and a certain concentration of the alkaline ionogenic silicate in any one chooses any ratio; for all of these variables are interdependent in a very intricate way. Even the effect of individual variables on the composition is quite involved. If, for example, the pH of the binders according to the invention is in the range -on. 5 VjIs 9.5 varies, one notices that the first ripening time initially decreases rapidly with increasing pH value, because a mini nnjua reaches it and finally increases again with increasing pH value. The speed of the initial analysis, dia X -ge of the minimum on the curve of the solidification time, and the degree of speed of the last increase as a puncture of the pH value are further influenced by the level of the neutral salt present; ilnfluBDt The Mindestmen each of the neutral salt present w3 ^ iru ruia is the Verhältnis.von silica ζ · alkali ι i. -The alkali see ionogenic: ien silicate determiicat. ⁱ

The gel time is also significantly influenced by which alkaline ionog-.ine Siiicat and what acid for! alinss; allung öss pH value of the agent solution is verv / enisto 3o iat the Ir-

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ORIQIHAL

The time of solidification is not the same for an organic ionic Silicate, like 'i'etraäthanolamnoimunsilieat, like for sodium silioate, and it is also not the same when using yon Acetic acid as when using sulfuric acid to neutralize. The larger the hydrated cation, the shorter it is is the solidification time, and “the higher the negative charge density on the acid anion, the longer the solidification time. which affects colloidal amorphous silica particles, which are contained in the sol from the start. The smaller the particle size of this material and. the higher the concentration iBt, the shorter the solidification time, at least if all the other variables mentioned above are kept constant ο If you do not take these relationships into account, you will succeed it may not even, arbitrarily, show it Amounts of silicates and amorphous silicic acid at arbitrarily chosen pH values are within the specified limits to mix together without premature gel formation and excessive salt contamination

i. form weak, worthless gels.

In vnifangreio ien investigations © wurcl found that regardless of the, -je / piece concentration of colloidal silica URV "i / eilcfr-vn. ^ R-IASE, regardless of Salsgelialt, the Kenge dee al \ Hli3üher ioiogenen silicates and the pK Value of Usutralisa-'eie: i and ui: fc.Mi'Jigig favon, which? Acid and welcres al ^ alischo iOi * j _c ene '-.''.- t verv.-enc ¹ et- will binders! * λιγα.Τ: _ -?, τ si \ ng i. ::? at 300 Seirnndeii cu S-elen solidify, öj: CCA ₁ -O) O j: - "ai-seic "u-btand as well as Baal: dea üiioclcie.a auasergeu'öl .-. 'lio" - ¹ . : ·: ■ · are i-ac a special, S-csssrs-; "s ·" ßefre:. · n: olstrv.kit-r "aufwerisen: 20 Isis 75 Gswicat ko? ·"oi.'lelt-.r · "ivhes £ .iliciu2jdio: -; ld alt oir.sm m ± - ctlere: i "che-" ⁱ IurchiBC-3 £ --c ;: from ^r . to 500 Εμ- X "to Y KoI dissolved a BCh3 £ ± ücc ^ / 'i c, silicate ^ e 1000 f BiiiScüritieltr lic'- > d - rg ^: Ι -: -: "-? ΛΜ1ο: ·; 1ά8 ₅ where;. iznd ¥ νχινϋ di

BAD ORiOtNAL

■ 1.9O- | (1.762 X = 10 * ""

3.70-1 (1.762 4

io ^J ■ "·

where 0 is the volumetric proportion of silicon dioxide in the support, JD is the mean partial ohmic diameter and S is the number of moles of dissolved cations, with the exception of hydrogen ions, per 1000 g of support, excluding silicon di-oxide, with the proviso that X is not smaller than 0.083 and Y is not greater than 1.67, and an amount of acid sufficient to give a pH of 5.0 to 9.5

Although one is aware of the general association just discussed Achieve solidification times between about 5 and 300 seconds can, in many cases it may be desirable to select particular solidification times within this wider range.

As already warned, the gel time depends on a certain amount Degree on the act of the salt (both the cation and the anion) which is present in the neutralization of the alkaline Forms ionogenic silicates. If ζ-.B, ■ as .. alkaline Ionic SiIi jar lithium silicate and to neutralize acetic acid use; becomes, ma »receives as salt LithiviriacötAto ■ Yerwezi det ican as alkaline ionogenic silicate Hatriru-siXicat Adjustment of the pH value of hydrochloric acid, so that it holds a & n IZo '/ as The expression :? Ir X and Y can be in the

Foriii verallgeia = become inert, whereby the KojiBtanttn K. and. K _{9 together} the sal:; effect. widerepiegalni

X or Y = IC- 1

The fourth of these constants are found in the JiachE jai table for ei / .e number of representative 'salts, and equations for X \ μ & T can be used for j; des especial HbXz uufgeetellt-

. '. "009811/1270

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by inserting the value of K ₁ '- for 300 seconds in order to obtain the lower concentration limit of the alkaline ionic silicate (X), and inserting the value of K ^ for 5 seconds in order to obtain the upper limit (Y) .

salt K ₁ (5 seconds) K ₁ (300 seconds) K ₂ KAc * 3.70 2.81 8.13 NaAc 3.73 2.84 8.10 LiAc 3.48 2.59 7.91 TAc ** 2.88 1.91 8.07 NaCl 3.46 2.57 7.87 Na ₂ SO ₄ 2.88 2.69 7.76

* Ac = acetate anion
♦ * T - tetraethanolammonium cation.

If setting times between 5 and 300 seconds are desired, the amount of alkaline ionic silicate required to achieve a particular set time can be determined by making use of the fact that the setting time is inversely proportional to the square of the concentration of the alkaline ionic silicate »This means: If the concentration of alkaline ionogenic silicate is doubled, the solidification time is shortened by a factor of 4 o If the concentration of alkaline ionogenic silicate β decreases by an actuator of 5, the solidification time increases by a factor of 25.

Using the equation for I and Y expressed by the above equation Relationships of the constant given in the table above, and the ob: .gen remarks on the action "of the alkaline Silicate on the solidification times is the laöhmann imstancle, for various alkaline ionogenic silicates, neutralizing seeds, particle sizes and concentrations of the colloidal amorphous silicon diocide, pH values and salinity

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BATH ORIGINAL.

even in this area with considerable accuracy, namely > 10 # to select specific solidification times.

In the previous description it was tacitly assumed that that gel formation takes place at room temperature, i.e. 25 ° G, and it is actually the most comfortable working temperature. The solidification time is of course very sensitive influenced by the temperature, and studies have shown that the temperature coefficient of the first warming time corresponds to an activation energy of approximately 20 Kcal., This means that for every 10 ° C increase in temperature, the time required for gel formation is halved. Served one looks at the classical equation of Arrheniue and the activation energy given above, the solidification time for any desired temperature can be in the range from 0 to 100 ° C from the values known for room temperature in a simple way Way to calculate.

The binder carrier according to the invention can be used on its own or in a mixture with particulate or fibrous fillers for the production of masses, which can be transformed into coatings for casting spans, paint-like coatings, other shaped products than coatings, e.g. molds for precision molding, and let the like convict. The relative proportions of binder carrier to particulate! or fibrous fillers can vary within wide limits and depend on the required degree of strength. The higher the percentage of the binder carriers according to the invention, the faster the resulting bodies are bound. It is usually necessary that the finished molded body consists of at least 5 percent by weight of its solids content of the binder carrier according to the invention. The amount of binder sluggish:?, Which is ^l required to achieve this solids content, can be readily prepared from the composition of the binder medium and the amount of faserföi'inigen binding to particulate or

- 18 -

00-9811 / 1270.

BATH ORIGINAL

Calculate fillers. Preferably, the amount of solids absorbed from the binder carrier is at least 10 percent by weight dee QeIs.

If the binders according to the invention are the main or only part of the finished dried body should be used, larger particle diameters and more concentrated Colloidal solutions of amorphous silica are used to prevent cracking and shrinking whenever possible suppress su. When the binders according to the invention ζ.Β «should be used as the only component, the partial ohendurohmessec of the colloidal amorphous silica is preferably more than 50 ΐημ and the concentration of the colloidal 3ilioiumdioxid3 in the carrier be at least 30 percent by weight. On the other hand, when the carrier is particulate or fibrous fillers in amounts of perhaps as little as 10 percent by weight To be mixed as described above, one can use lower concentrations of colloidal amorphous silica and use smaller particle sizes, e.g. the lower ones Limit advertising of 20 percent by weight of the binder solution < or particle sizes of 5

Almost any particulate or fibrous material can be used bind with the means according to the invention; the choice is not critical, except insofar as the properties of the additives can affect the end use. For example, if the finished bound K8a? Per is used at high temperatures should be: if you choose a filler that is heat-resistant, particleförffi ± £. s material that has a sufficiently high sohicel point hat.tmd. is sufficiently consistent to meet the expected Conditions ar> to be adhered to. For the production of molds for the Precision casting of metals can be made amorphous Silicon d.1 oxide grains. Zircon, mulite or similar substances with use very high melting and softening points = for others Uses such as insulating paper or heat-resistant papers or masts, heat-resistant fibers can be tied together. Such fa-

- 19 -

00S811 / 127G BAD ORIGHNAL

4176-G <λθ

B.oB »can be made from asbestos, glass, rock wool, aluminosilicate consist} one can also use pure amorphous silicon dioxide fibers or Fibers or tips made of boron nitride, silicon carbide or nitride, aluminum oxide, metallic boron, carbon and other substances fen use o The carriers according to the invention can also Additives such as dressing agents, anti-foaming agents and the like, added pasture,

As can be seen from the above description, the binder carriers are according to the invention by the concentration of the alkaline ionogenic silicate, the concentration and the particle diameter of the "colloidal amorphous silicon dioxide and the pH. The concentration of alkaline ionogenic silicon dioxide and amorphous silicon dioxide contained in the original sol can be obtained by using standardized

weighed quantities of known concentration predetermined or they can be determined ν by using the binder solution The silicon dioxide concentration of alkaline ionogenic silicates can be analyzed in a known manner according to the colorimetric molybdic acid method described above will. The concentration of the colloidal amorphous silicon diocide ka: can also be determined by separating it from the alkaline ionic silicate by dialysis and the amount of colloidal amorphous silicon dioxide on gravimetric © !!) Paths determined. The colloidal silicon dioxide can also be determined " by r.an daa alkaline ionogenic silioate with the help a mixed ion exchanger then removes the concentration des colloidal en. Silicon dioxide, through the ion exchanger through it, determined in a more grsvimetric way <> The pH of these solutions can be adjusted in a more well-known manner Glass electrode and a pH measuring device or? naa'-i ^ every other method which are used to determine the Öeo pE value of aqueous solution is known »Der 'Seiletendv.reiifliee8er des colloidal amorphous silicon dioxide ^ can be obtained by counting the particles on ptotographi-

- 20 -

009811/1270

see recordings can be determined, or it can be determined on the isolated colloidal amorphous silicon dioxide after its separation from the ionic alkaline silicate by acidification to a pH value of "5 or less and drying from the apical surface of the dried material, which in turn is determined by nitrogen adsorption o The mean particle size can be calculated from this specific surface area and the density of the amorphous silicon dioxide, assuming that the particles are uniform spheres o Another method for determining the specific surface area after the alkaline ionic silica has been separated off is litration of the silanol groups in the presence of concentrated saline solutions as described by G _s ¥ _e Sears in "Analytical Chemistry", Volume 28 _} 1956, page 1981

The important characteristic features of the gels according to the invention are the particle diameter, the density, the mean pore diameter, the pore size distribution, the percentage porosity and the mechanical strength. After the gels have dried and heated to a temperature not exceeding 600 ° C, they can be determined from the specific surface area determined by nitrogen adsorption is by examining the sand of the irregular lumps of gel. However, the particle size can be determined jSol AUOH in cam ale output material used amorphous colloidal Eiesel3äu'c because the solidification process itself, the Tel-size in, not change, not heated when die.Produkte to temperatures above 600 ° C. The density and the percentage Po Osität can after each Yerfahran determined advertising • the wherein m in dae of a portion of the gel volume occupied and daa Gedcht thereof determined simultaneously. This can ZoB. done by ini-is the volume by displacement of mercury and the weight on an analytical balance

009811/1270

certainly. The mean pore diameter and the pore sizes ~ distribution can be done in a known manner with the Queokeilber porosimeter or curoh gas absorption can be determined. The determination The mechanical strength of the gels of the invention can be made by using the cross-pausing facility or measure the tensile strength using known methods.

The process according to the invention is usually carried out by mixing an alkaline ionic silicate with a solution of amcrpher colloidal silica, adjusting the pH to the desired value within the range of 5 to 9.5 by rapidly adding an acid and about 5 Waiting for up to 300 seconds for a gel to form Mix the shaped fillers to make a rounded product. If a binder carrier with a long setting time is used, the filler can also be added after the pH has been adjusted; This - method is not preferred, however, especially since-ua if products are not to be made by exceptionally homogeneous in nature.

When mixing, certain precautionary measures should be taken. When the solidification time is short. must iaan s? hnello use mixing methods / This can be achieved on different Ysiee »eg with the help of Mischdüacm, öiirci. / sraiacten with very tendons ..! running Hührern iia Waring-KijcJr.e ■ j the ii \ the colloid mill, e or by mixing the? Currents i-, -äylinder '. a Spritzpiitole in a turbulent Stask SereiJh, dsr OIV vo immediately: ^j is the outlet of the Spritsjpi stole α ζϊο order for the compositions according to the Erfindjng ^ oharakterietisciia hoi & ogeno to achieve structure Mschzeit may only be a fraction of

- 22 -

009811/1270 BAO ORIGINAL

the period of solidification. If you want to work in the shortest Eretarrungszeitciji in Gröseeiiordnung 5 seconds, this mixing times erfordeit in -the order of. maybe only 1 second or less, e.g. was achieved in mixing nozzles.

Although it is usually necessary to mix the relatively large amounts of alkelic ionogenic silicates which are required for the compositions according to the invention directly with the colloidal anorphous silica sols, such mixtures sometimes prove to be inconsistent, in that they are ready to coagulate or flop out before the neutral earth acid can be added. There are several methods that can be used to avoid this. One method is to first mix the neutralizing acid with the colloidal amorphous silicon dioxide and then add the alkaline ionic silicate in the last mixing stage. Another method consists in first mixing the acid with the alkaline ionic silicate and then adding the colloidal amorphous Siliciaadioiid. One can also add the neutralizing acid to one part of the colloidal amorphous silicon dioxide and the alkaline ionogenic silicate to another part of the colloidal amorphous silicon dioxide and then combine these two mixtures with one another immediately before application: this is very difficult when applying coatings Spray on, because you can then mix the same parts of liquid with one another immediately before the spraying process, without having to make use of cumbersome measuring devices =

The pH value äs. ' The fastest formation is in the range of about 6 to 8 years and the whisking process should be carried out in such a way that the binder is in this critical pH range for as short a time as possible, as soon as the components have only been mixed homogeneously with each other.

- 25 -

009811/1270 ORIGINAL BATHROOM

The gels so obtained do not instantly develop the full gel formation their full wet strength. Eb it has been found that approximately ten times the initial gel time is required to ensure that all polymerizing ingredients are in the binder carrier have united to form a gel network. It is therefore usually expedient to keep the gels as suppressed as possible evaporation of water from the gel at least ten times as long to age as required for initial gel formation was ο

If you want to make the toughest gels that can be obtained It is often beneficial to use the gels after aging subject to further heat treatment or autoclave treatment, The higher the temperature used for 4 heat treatments the less time it takes for the gel to solidify further. According to an advantageous process the gel is solidified by placing it in an atmosphere of live steam is introduced, or, if even higher temperatures and shorter times are desired, by placing it in an autoclave under pressure is treated »

Often it is found that by adding a small amount of fiber material t such as asbestos, cotton linters, Papiersellatoffmasse and the like, oiler tchenförmigen by the Zusetz a plae + material, such as mica, kaolin, clay, talc -etc., The inclination of the gels, jumps train wheel consequently shrinking forces /, "can be lert much vermin ■" if heat resistant we molded articles produced ".-the should be substances vie'Tapiersselletoff or BauKiwolliMters can use 3elbst when a the Pormiörper burned schliecoLioh & \\, since these substances solidify the structure during the critical period when the solvent is first removed.

It is also for the purpose of tying the tailehenföraigeix To use filler in classified grain sizes and in that

- 24 -

' 009811/1270

BAQ

Mixture from which the molding is made to achieve the highest possible solids content »By making the right choice of the grain sizes using known classifying methods, it is possible to obtain molding compounds that only shrink very little.

Jumping is a dynamic stress-reliever and is determined at least in part by the speed at which the solventB is removed from the structure of the violin of the gel network, the magnitude of the force resulting from this shrinkage depends at least in part on the drying speed. In general, it is therefore necessary to dry the molding compounds according to the invention as slowly as possible, taking into account other factors such as economy. Compositions according to the invention, by adding won faseiförmigen 3The platy Stoffan, by using "/ on Mtzebe3täadigen substances with a particulate sized or duroh heating in an atmosphere of water vapor, or after all: have been i these methods, solidified as described above, are less sensitive to the speed of communication and can usually be dried very quickly; i

The following examples serve to further explain the masses and the method according to the invention, in which 0, P and £ J have the meanings given above »

B e i a pi e 1 1

90 Si, v / ichtstoi: .e of an aquaeol, which is equal to 30 percent by weight

colloii-ale aaorplie silica parts with a ^ eii. Jtorol-meBBer of 7 ιπμ contains, are mixed with 4.1 weight of 6 η sulfuric acid. An approach of the

OOSIti / UTO BAD

1329712

acidified aquasols containing 20 parts by weight of silicon dioxide, is made with 80 parts by weight of refractory amorphous silica grains mixed that to 55 # by a sis "b egg 0,» 49 psr Pass through the mesh and from a sieve with 0.074 mm mesh be withheld and to $ 45 clutch an Oiet> isi.t 0.044 mm mask width go through.

This mixture is added in the manner described below TuAi, a sufficient amount of a solution of sodium silicate (grade "F") containing 30 percent by weight of SiO ₂ (i.e. 5 molar of silicon dioxide) to give a 0.602-molar silicate concentration , based on the amount by weight of the total volume, exclusively of the colloidal silicon dioxide and clear heat-resistant grains. The sodium sulfate is added to the Maus® 3i; .g & 33t [, t _; by introducing the two substances separately under pressure into the stage of a very smoothly running stirrer in such a way that the required mixing time is only about 1 second. The mixture obtained in this way has a pH value of 8.00, a j # value of 0 _? 60 and an S-value of 0.302 and vjii'l soi'ori ir the cavity of a Porm injected The Gemisch..e: eßtai * rt iii about 8 secondary _(n to a gel ·

The gelled (-emisch is in the form of still 80 Hekun'lan altsxn left and then i st tight enough so that the lovm can been removed. The Farm negative thus obtained is treatable fe-15 minutes at 125 ° C under sutogenem Waeserdaiapfdruck in an autoclave, then tumbled and finally burned at 800 ^!> 0 for 60 minutes;

The fired mold negative is used as a mold for casting in the manufacture of castings

Steel used. Shape and dimensions of the primordial ^ fora

are used in the juss without distortion and with good reason Reproduced tolerances.

- 26 -

009111/1270

Example 2

332 g of an Ao.uasole that 55 * 67 percent by weight colloidal amorphous silicon dioxide with an average particle diameter ™. water of 112 m \. contains, Dae mixed with 117.6 g of distilled water are obtained in this way using a Sohnell stirrer with a solution of 61.2 g of sodium silicate (SiO ₂ : Na ₂ O ratio = 4.5: 1) in 28.8 g of Waoeer mixed «In the mixture, the molarity of the silicon dioxide due to the sodium silicate is 0.480 and the holarity of the sodium ions is 0.2016. The mixture has a £ 0.163.

Three batches of this mixture to each 90 g with 1.5, 1? 4 and 1.25 ml tines mixture auo same parts of acetic acid \ n \ ä water to pH ~ tferte of 6.5, or 7.8 7t0 . The solidification side of the three solutions is 170, 98 and 186 seconds. The gels are aged in a period equal to the 240 times their solidification times, the evaporation of water being prevented by keeping the gels in a vapor-tight, uncompromised Rajun

The aged gels will last 2 weeks * - *. ^ «». Vacuum dried, whereupon the specific surface (by nitrogen adsorption), the density and the transverse breaking strength are determined. The specific surface j is 26, 26 or «. 28 mVs "while the specific upper!" Pool of the sol from which the gels were made is 22 id * / g. The densities are 1.22, 1.25 and * 1.22 & / οκ \ was 53, respectively * 0, 53t5, or 53.0 $ of the theoretical density doo kol oidalen amorphous Siliciu3idioxide corresponds to "HXE _{Querbruchfesti;;} kQiten the sample amounted to 105.5, 112.5 or '126.5 kg / on _a ^2" ■■■ ■■ -. * "■

The three gels are then heated for 1 hour to 600.degree. C., whereupon the specific properties determined by sticket material absorption? flat and the density have not changed. The transverse breaking strengths are now on the order of 133.6 to 16ST kg / om. "

-: 27 -

The pore size distributions become on the gels after heating determined to 600 ° C «. It is found that the middle Pore diameter in all cases is approximately 60 πιμ and the pores are extremely homogeneous, in that more than 90 # of the pores have diameters between 30 and 70 μm. As a result of Combination of high strength, especially after firing at 600 ° C, and the large and even pore diameter these gels are excellent as catalyst supports, supports for diochromatographic separation and supports for separation organic polymer fractions of substances of lower molecular weight.

The gels are again heated for 1 hour, this time to 1100 ^° C. The densities of the samples are now 94.8, 97.8 and 98.3 1> the theoretical density. The transverse rupture strengths are in the range of about 281 to 351.5 kg / om ". This strength is to be described in comparison with handelüüblichen quartz glass to be favorable. In view of their strength" density and ease of processing are these gels especially VCN for producing refractory shaped bodies _t

Example 3

The procedure is as in Example 2, but instead of άοα sols with part sizes of 100 μm, the same amount of a colloidal silicon dioxide sol with an average particle diameter of 50 μm is used. The density, strength and continuous properties of the gaIe obtained in this way are similar to those of the Ge'.e deB Example 2 "The .mit tiere poreniur chinese ex after heating to 600 ° C is 29 mn - but the pores are in this case" ^ even higher, in that only? C ^ of the pores are larger than 30 ναμ and with 10 J6 smaller than 20 κμ, 85 $> the pores lie within a range of «5 ιεμ% on the medium pore size

- 2-3 - ■

009811/1270 BAD '

Example 4

This example illustrates the preparation of a sprayable ceramic mass that can be used to make ceramic coatings and porms for precision die casting of molten metals. Two mixtures are made with 0.149 mm mesh size and held back by a Siob.with 0.074 mm mesh size and pass 45 Ί » through a sieve with 0.044 mm mesh size. The first mixture also contains 1100 g of amorphous silicon dioxide oil with spherical particles with an average diameter of 12 μm and a silicon dioxide content of 28 percent by weight. This sol is prepared by mixing 43.4 parts by weight of water with 100 parts by weight of a 40 percent dispersion of amorphous silica and then adding the following: 0.184 parts by weight of a polysaccharide-based dispersant ("Kelzan" available from Keled Co., Clark, New Jersey, VoStoAo), 0.2 parts by weight of bentonite, 2.68 parts by weight of ethylene glycol, 6.24 parts by weight of dipropylene glycol, 0.134 parts by weight of polyoxyethylene wetting agent and 0.14 part by weight of a silicone-based SohauiH wetting agent. 1100 g of sol was a mixture of equal parts of glacial acetic uad Wa ₁ SSER mixed with 66 al, whereupon the above-mentioned 1,980 g hitse'be constant S -liciuiadioridkörner zusetzte The mixture thus obtained iIAT et ien pH of 4.1 and such a viscosity that it passes in 3 "b:, s 9 selomden through a cup of Ir. 5 of the tooth.

iθ f.5v / © its hair is made by adding 1900 g of the above mentioned hl ta. stable silica grains, 1070 g of the above mentioned sulfur dioxide sol _: that the versohitileneji Z \ w ^; tze contains, 330 ₄ | mix a 12 percent aqueous 3N solution of tetraethanol dinonium silicate and 100 ml of water =, "The z \ '< : ite mass has a ^ n pH value of 11.4 and runs

009811/1270 BAD ORIGINAi

through a # 5 cup of the dental viscometer in 7 seconds through. The molarity of silicate ions is 0.294 mol each 1000 g of the total mixture excluding the weight of colloidal silicon dioxide and heat-resistant burners. The molarity of tetraethanol ionium ions is also 0.294.

The same clearing parts of each of these two compositions are put into the two 7.57 l parts of a double pressure vessel which is connected by pressure hoses to a spray gun in which there is a mixing chamber immediately in front of the nozzle, in the mixing chamber is a high-speed stirrer arranged, which is driven by an air motor attached to the butt of the syringe gun. When the stream from the two containers met in the mixing chamber, they are mixed with one another by the guide, and the Qsxäi.wh. is immediately atomized into a fine spray jet.

The spray jet has a pH value of about 6, a ijojöha thixotropic viscosity and solidification so that there is only insignificant flow on the sprayed tunnel. Within 30 seconds it freezes on a; tar.? en Ce ?. In the absence of the minor Menga Tetraät ^v tanolaamoaiXisilic £ .i; this spray jet would not e- --y'cavz'en u ".3 for coating after the spray method wsr'clos leg for many hours

"The duroh spraying diesel * Hasae in dan ve-rachje -! -.> ._ ■ csr. 3er, r. Produced keraidachen Siliciumdioiid-ioi-aiajrpsr Jrö? I; χ. Χ di? Air dried · and at temperatures up to 000 ° C g => - ".. 'K-isii ί * ε <, ^ & .. ·. where s © in .f cats ,, hard porous *> Mass axa sixi ο V ... rl Überg3hen _s which Aehr good for ^Her3telli: J. g vo ". l & r sri; - '

Bodies for a wide variety of ts ramisohan dormin »Tim Cries3en from gesohmoAi'.e; ioii Kota" on,

- 30 - ■■ 00981171270

SAD ORIGINAL

Examples 5 to 18

The series of mixtures given below is produced in order to show the influence of the selection of the pH value, the values on 0, S and D as well as the alkaline ionic silicate on the solidification side. Acetic acid is used for neutralization in all cases.

- 31 ~ 009811/1270

example

5 6 7 ο

10 11

ü 12

15 16 17 18

Colloidal silicon It dloxid "0" Silioate cation Holare Kon
centering PH S. Paralysis
time, sec. Il 0.156 lithium 0.390 9.2 0.220 76 "D" 17th ti Il It 8.5 It 38 12th H Il Il π 6.55 It 71 ι » 18th u, uyb Il 0.86b 9.8 0.684 8.5 dd Il • I dd η 5 * 8 Il 24 »I. It η η 5.3 η 42 11.2 0.239 Tetra
ethanol
ammonium 0.100 6.4 0.070 47.5 Il Il π η 8.0 It 300 ti 0.155 sodium 0.466 7.9 0.233 40 Il ti It 8.5 It 85 Il Il It 8.8 ti 275 0.163 ti 0.480 6.5 0.202 170 Il It Il 7.0 Il 98 ti η It 7.8 It 186

Claims (1)

Claims 1. Mass »characterized in that they (a) from 0 to 95 percent by weight of a particulate or fibrous filler and (b) from 5 to 100 percent by weight of an aqueous binder vehicle which in turn contains 20 to 75 percent by weight of colloidal amorphous silicon dioxide an average particle diameter of 5 to 500 ιημ, X to Y moles of dissolved alkaline ionic silicate each 1000 g carrier excluding silicon dioxide, whereby X and Y by the equations 1.90-f (1.762 + ^) -f + ζ p X β 10 : 3.70 »| (ΐ» 762
Y = 10 ^ ~ are determined, in which 0 is the volumetric proportion of dosed silicon dioxide in the carrier, D is the mean partial ohendur Jlimessör and S is the molar number of dissolved cations with the exception of hydrogen ions per 1000 g carrier excluding silicon dioxide, with the proviso that X is not less than 0.063 and Y does not al3 I ₃ S / eats large, and contains such an amount of acid that the pH fert ^v of the carrier in the range of 5 »0 to 9.5, - 33- ' 008811/1270 4176-0 3Ψ 2. Composition according to Anspruoh 1, characterized in that X is not less than 0.167 and Y is not greater than 1.00. 3. Hasse according to claim 1, characterized in that the alkaline ionogenic silicate potassium silicate, the acid acetic acid and X and T are determined by the following equations will: , 762 X «· 10 ' Γ _2, 81- | (1, [3,70- | (1.762 [3,70 | (, 7 §> -f ♦ y = io 4. Mass naoh claim 3, characterized in that X is not less than 0.167 and Y not greater than 1.00 iat. 5. Composition according to Anspruoh 1, characterized in that the alkaline ionogenic silicate sodium silicate, the acid hydrochloric acid and X and Y are determined by the following equations will: !, 57-5 (1.762 Xs 10 ^L -J j (1,762 Y a 10 ^ 6. Composition according to claim 5 »characterized in that X is not less than 0.157 and Y not greater than 1.00 iot. 7 «Composition according to claim 1, characterized in that ο the alkaline ionogenic silicate, methyl silicate, and the acid acetic acid and X and Y are determined by the following equations warden: - 34 - 00i811 / 12f0 r ~ 2.59-f < 1,762 X - = 10 1.762 + 8. Composition according to claim 7 * characterized in that Σ niofct less than 0.167 and Y is not greater than 1.00. 9. Silica gel, characterized in that it is 0 to 95 Gewiohtsprosent from a particulate or fibrous shape gen filler and at least 5 percent by weight eub amorphous colloidal silica particles with a medium Partial diameters from 5 to 500 βμ breathed, vobci the colloidal Silicon dioxide partitions by 0.5 to 10 percent by weight polyaerized alkaline lnogenic silioate in Form of a porous, 'three-dimensional chain rigid with one another are connected. 10 «Silica gel according to claim 9», characterized in that the mean particle diameter is at least 50 w \ i . 11 silica gel, characterized in that 0 to 95 percent by weight of a particulate or faserföriuigen filler and at least 5 weight percent of amorphous colloidal silica te union having a mean. "Teilchendurnhmesser from 5 to 500 MJI is, woboi the diameter of substantially all colloidal silicon dioxide particles are 0.8 to 1.2 times the mean diameter, the colloidal silicon diocide cells are rigidly connected by 0.5 to 10 percent by weight of polymerized alkaline icnogemes ensiled in the form of a porous, three-dimensional Netsea, which have a diameter of at least 60 of the pores in the hot spot are 0.8 to 1.2 times the mean particle diameter, the mean pore diameter is 0.5 to 1.5 times the mean particle diameter. '- 35 - 009811/1270 ORIGINAL BATHROOM diameter, the pore volume of the network is 45 to 75 # of the agitation volume and the transverse crushing strength of the gel is at least kg / cm ² . 12c silica gel according to claim 11, characterized in that that the mean particle diameter is at least 50 ηιμ ". 13c Process for the production of shaped products, characterized in that one
(1) deforms a mass that (a) from 0 to 95 percent by weight of a particulate or fibrous filler and (b) to 5 to 100 percent by weight of an aqueous Birdemittelträger, which in turn 20 to 75 weight percent colloidal amorphous silica with an average particle size of Güei '. 5 Mi 500 ΐημ, Z to Y moles of dissolved alkalisohaa iorogenic silicate per 1000 g carrier exclusively dee silica, where X and Y by the equations 762 X «10 ^ 10 j ~ U90-f {i,
[3.70-f (1.762 ■ be determined where 0 is the voluinetri & casit Κν-Λαχΐ of the silicon dioxide in the carrier, D is the average particle diameter and S is the molar number of cations with the exception of the Vassers-tofiionaii ^ c 1000 r carrier excluding the silicon ;; - ? .Is \ λλ \ ζ \ ϊ - ^ r -.- with the addition of mass that Σ is not less than a'e O ^ Oe-i u:> 6. Y is not greater than 1.67, and contains such a Nei, ^. · Acid that the pH of the carrier : .m 3-t; - rice is from 5> 0 to 9.5, and - 36 - \
009811/1270 BATH (2) the mass in the desired shape for a time sufficient to gel from 5 to 300 seconds holds. 14a method according to claim 13 »daduroh characterized in that X not less than 0.167 and Y not greater than 1.00, 15o method according to claim 13, characterized in that one as alkaline ionic silicate potassium silicate, as Acetic Acetic Acid is used and X and Y can be determined by the following equations: 2.81-f {i, 762-5 X = 10 - [~ 3,? 0 ~ fc 1.762 Y * 10 ! β »Method according to claim 15, characterized in that X not less than 0.167 and Y not greater than 1.00 * 17. Ancestors according to claim 13, characterized in that one as alkaline ionic silicate sodium silicate, as acid Hydrochloric acid is used and X and Y by the following equations be determined: . I 2.57-f (i, 762 -5- X s 10 L- M, 46- | (1.762 + Y * 10 ~ * ίθο decay ron η i. Claim 17, because it is known that Z is not less than 0.167 and Y is not greater than I ₉ OO let " 19o Vsrf-ahriän Rich Anapruch 13, 'daduroh characterized that one al8 alkalis; hes ionogenic silicate lithium constituent, as acid esous acid / used and X and Y by determining the following equations: -37- 009811/1270 BATH Γ- , 762 X s-1O ^r Y - 10 ° 20o ve.T '£ anx'en according to claim 19, characterized in that daes G small? ale 0.167 and Y not greater than 1.00 ia-fe - 38 -: 000111/1270 6ADORJQtNAL