JPS6158420B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to filled inorganic plastic cements in a solid or expanded state, compositions and methods for forming them, and more particularly:
The invention relates to an inorganic plastic cement filled with magnesium oxychloride or magnesium oxysulfate which has good bending strength and is also water resistant, non-hygroscopic and natural. Magnesium oxide cements, commonly referred to as inorganic plastic or plastic cements, are known. An improved method for producing these inorganic plastic cements (magnesium oxychloride and magnesium oxysulfate) is described in U.S. Patent No.
It is written in No. 3320077. These inorganic plastic cements find use in the production of molded or cast structures, such as construction panels, brickwork, flooring, etc. and protective coatings. Due to the unique properties of improved inorganic plastic cements, in particular:
Because of their nonflammability, these materials have more potential uses than traditionally expressed. Such potential uses include bathroom fixtures, bulk transport seating, aircraft interiors, office machinery and equipment housing, seating in stadiums and other public facilities, interior paneling for trucks and buses, furniture, etc. I can do it. In these potential applications, unlike applications such as construction panels, brickwork, flooring, etc., the structural material must have some degree of bending strength. Enriched magnesium oxide cements without fillers and magnesium oxide cements filled with powder materials and/or standard length glass fibers are relatively hard and susceptible to crack formation in the magnesium oxide cement matrix. It exhibits only limited shear strength in directions where there is little or no reinforcing fiber to prevent crazing of the surface of the matrix. Such crazing begins as microcracks, and if this crack growth is not stopped, the microcracks will continue to grow until the flexural, tensile and structural strength of the product formed therefrom is reduced below acceptable levels. do. The same can be said for surface crazing. Of course, a wide range of technologies exist for filled synthetic resins and plastics, such as filled polyesters and epoxy resins, which are widely used today in many different applications. However, this technique for filling synthetic resin cannot be directly transferred or applied to inorganic magnesium oxide cement. The reason for this can be considered to be the fundamental difference between these inorganic plastic cements and organic synthetic resins. One of the more important of these differences is that what is commonly referred to as "modulus" (defined as the slope of the stress-strain curve) differs from that of polyester or epoxy resins alone compared to glass fibers (or other reinforcements). The fact is that it is considerably lower than that of the material. For example, the modulus of polyester resin is approximately 21000~42000Kg/ ^cm2 (300000~
600,000 psi), whereas the modulus of glass fiber is 700,000 Kg/cm ²
(10000000psi). Therefore, the resin in the filled synthetic organic resin system acts as a reinforcing agent,
The present invention provides a matrix structure that can convert the stress applied to the glass fiber filler, which takes on stress beyond the point at which stress failure would occur with resin alone, into a slight strain. Unlike synthetic resins, magnesium oxide cements have high modulus values in the same range as fillers. Typically, the modulus for unfilled magnesium oxide cement is approximately 140000Kg/cm ²
(2000000psi). This means that the magnesium oxide cement in the inorganic plastic cement-glass fiber system cannot deform under stress and transfer the load applied to the long glass fibers without fracture and initial failure of the cement matrix. It shows. As will become clear from the detailed description and data provided below, it is therefore not possible to use magnesium oxide cement as a substitute for synthetic organic resins in known organic resin-glass fiber systems, and It can also be used to form many of the currently used filled magnesium oxide cements for synthetic organic resins and still obtain optimal or acceptable properties.
It's impossible. The fact that magnesium oxide cement is water-resistant and natural and the raw material costs for its production are lower than in synthetic organic resins lies in its solid or foamed form, which has good flexural strength. The ability to provide modified, e.g. filled, magnesium oxide cements thereby significantly widens the range of applications in which these inorganic cements can be used, and in many applications renders them non-combustible. It would be desirable to be able to use them in place of synthetic organic resins. Therefore, the main object of the present invention is to provide an inorganic plastic cement in solid or foamed form, i.e. in foamed form, which according to the invention has a uniform cell structure and an adjustable and predetermined density. It is another object of the present invention to provide a filled inorganic plastic cement, in solid or foamed form, which combines flexural strength, tensile strength and impact strength, thereby making it suitable for many applications. In this case, it becomes possible to use such a filled inorganic plastic cement instead of a filled synthetic organic resin. Still other objects of the invention include panels, wall panels, structural elements such as bathroom fixtures, mass transit, stadium and other public facility seating, aircraft interiors, office machinery and equipment housings, truck and bus interiors, furniture, etc. The objective is to provide water-resistant, natural materials for the construction of a wide variety of items, including, but not limited to, protective layers. Another main object of the invention is to make it possible to use filled inorganic plastic cements instead of the currently used filled organic resins, especially in many applications where non-flammability is important. To provide a composition for forming a filled inorganic plastic cement, in particular a filled magnesium oxide cement, in solid or foamed form, for use in producing a filled inorganic plastic cement with flexural, tensile and impact strength. be. Yet another principal object of the present invention is to provide an improved method for forming filled inorganic plastic cements in solid or expanded form. It is an additional object of the present invention to provide an improved method that makes it possible to form filled inorganic plastic structures by molding, compaction, lay-up techniques, and the like. Other objects of the invention will be partly obvious and partly apparent below. In one aspect of the invention, a magnesium salt,
forming a reactive aqueous slurry consisting of a water-soluble phosphorous oxide and magnesium oxide having a viscosity in the range of about 700 to 15,000 centipoise; of a microfiber filler in an amount such that the microfiber filler is nonplanar and multidirectional in the resulting filled inorganic plastic cement. is provided. Addition of a filler additive, a gaseous component capable of foaming the slurry during or after the addition, to the reactant slurry will cause foaming to occur to form a foamed product with a uniform cell structure and a controllable predetermined density. resulting in the generation of a slurry that can be used. In another aspect of the invention, the magnesium oxide cement and the magnesium oxide cement have a
A filled inorganic plastic cement is provided in combination with a multidirectional microfiber filler present in an amount of about 40% by weight and in solid or expanded form. In a preferred embodiment of the product of the invention, the magnesium oxide cement is magnesium oxychloride formed from a reactive composition that does not contain any appreciable excess of water that must be removed by evaporation; The fiber filler is present in the range of about 5% to about 20% and is milled glass fiber, substantially all of which passes through a standard American 1/4 inch (6.35 mm) sieve. One or more secondary fillers may also be incorporated into the filled inorganic plastic cement. Such secondary fillers include long fibers, particulate materials and glass fiber mats. For a more complete understanding of the nature and objectives of the invention, reference should be made to the following detailed description taken in conjunction with the accompanying drawings. The method of forming the filled inorganic plastic cement composition of the present invention is preferably carried out up to a certain point in accordance with the method of U.S. Pat. No. 3,320,077. That is, high speed,
Preferably, high shear mixing is used. The method of forming the composition therefore consists of the following steps. The method of the invention as applied in the case of producing a fully filled inorganic plastic cement is illustrated in FIG. Therefore,
First, the production of a fully filled product will be explained. The magnesium salt used is magnesium chloride, MgCl ₂ 6H ₂ O, used as the hexahydrate, or magnesium sulfate, used as the heptahydrate.
It can be either MgSO ₄ .7H ₂ O. The first step in the process of the invention is the formation of an aqueous solution of the magnesium salt. This solution, called the gauging solution, may be supersaturated with magnesium salts,
It is also preferable to form the film so as to contain a small amount of water-soluble phosphorus oxide. In preparing the gauging solution, the weight concentration of the magnesium salt (in hydrated form) in the resulting aqueous solution is about 60 to 80%, preferably about 70 to about 75%, based on the total weight of the hydrated salt. should be within the range of The roles of water-soluble phosphorus oxides appear to be diverse. This improves the wet strength of the resulting filled inorganic plastic cement, helps adjust the viscosity of the liquid reaction composition within the desired range, sequesters chelating chemical ions in the reaction system, and decomposes the magnesium oxide. It is believed to aid aggregation and prevent crystal growth. Among the water-soluble phosphoric oxides that can be used are phosphoric acids, polyphosphates and also "glassy" phosphates, in particular the so-called hexametaphosphates, various alkali metal monobasic and dibasic phosphates. , ammonium phosphate, etc. The term "sodium hexametaphosphate" is used in the following, following convention, when the molar ratio Na ₂ /P ₂ O ₃ is
A number of glassy chain phosphates are used to encompass a number of glassy chain phosphates which can range from about 1 to about 1.5. The amount of water-soluble phosphorus oxide used can be up to about 6% by weight of the added magnesium oxide, with a preferred range of about 1-4%. Although either phosphoric acid or glassy phosphate may be used alone, it has been found that for reasons that are not yet clear, it is preferable to use these water-soluble phosphoric oxides in combination. Although any combination of these phosphoric oxides can be used, a 2:1 phosphoric acid:vitreous phosphate weight ratio has been found to be particularly effective in producing the final microfiber-filled inorganic plastic cement. . Although phosphoric acid is soluble in magnesium chloride solution, glassy phosphates, such as sodium hexametaphosphate, are not. Therefore, if a glassy phosphate is used, it is necessary either to first dissolve it before adding the magnesium chloride, or to dissolve it in the phosphoric acid; in this latter case, A solution of both of these phosphorous oxides may be added to water either before, simultaneously with, or after the addition of magnesium chloride. The magnesium oxide used can be either natural or synthetic, with natural being preferred as it appears to provide a packed structure with somewhat higher bending strength. A preferred form of magnesium oxide has an iodine value of 15 to 60 and 50% of
The particle size distribution is such that the particle size is less than 0.3 microns and substantially all are less than 20 microns. The amount of magnesium oxide is related to the magnesium salt used to form the inorganic plastic cement. When using magnesium chloride, the molar ratio of MgCl ₂ 6H ₂ O:HgO is approximately 1:
3 to 1:9, but when MgSO ₄ .H ₂ O is used, the molar ratio is about 1:3 to 1:14.
This is MgCl 2 6H ₂ O in the case of _MgCl 6H ₂ O
The weight percentage of MgO to the total amount of MgO and MgO is approximately
can range from 37 to 64%, while
In the case of MgSO ₄ .7H ₂ O, this means that the weight percentage of MgO relative to the total amount can range from about 33% to about 70%. In the formulation of inorganic magnesium oxide cements with the addition of microfiber fillers, a reactive aqueous slurry containing no appreciable excess of water that must be removed during solidification and hardening of the solid inorganic plastic cement is used. Gauging solution concentration and MgO as generated:
Preferably, the ratio MgCl ₂ .6H ₂ O (or MgSO ₄ .7H ₂ O) is chosen. Essentially, by using only that amount of water that participates in the reaction to produce the final inorganic plastic cement, there is essentially no excess water present that would produce Mg(OH) ₂ . The quality of the cement can then be maintained at the highest level with respect to parameters such as, for example, the strength, water resistance and uniformity of the product. Magnesium oxide is added to a magnesium salt solution containing phosphorus oxide. It is preferred that the magnesium oxide be added gradually, and it is important that the slurry be treated in a high temperature/high shear blender during its formation to deagglomerate and thoroughly disperse the magnesium oxide particles. The use of extremely fine magnesium oxide and its complete dispersion for reaction with magnesium salts
Produces a slurry of low viscosity. Thus, the quality of the magnesium oxide is an important contributing factor to the final filled inorganic plastic cement. As already mentioned, the role of the filler in the filled magnesium oxide cement does not appear to be solely as a reinforcing material. Due to the properties of magnesium oxide cements (high modulus and relatively low flexural strength), these cements are not included within the meaning of the term "filler" as used herein, but may be partially self-contained. It can also be said that it plays the role of a filler. This therefore also means that the filler added must be of such a nature that it contributes to the flexural strength as well as the tensile and impact strength. To that end, the filler must be non-planar, i.e. it is a material such as long glass fibers, or indeed a relatively large platelet or finely granular material that provides two-dimensional reinforcement. It shouldn't be. The filler of the present invention can be different from that in a number of directions, e.g.
It must be sized and shaped to provide additional strength in the direction. Therefore,
For convenience, it is referred to as "multidirectional" to point out that the filler is non-planar. In order for a filler to meet such non-requirements, it must:
It is necessary to contain sufficient short fibers to enable multidirectional placement of sufficient amounts of filler. Generally, such short fibers, referred to herein as "microfibers", have a diameter of about 0.6
Should not be longer than ~0.7cm. These microfibers, which act as fillers and have a multidirectional arrangement, can play the dual roles of filler and matrix, thus creating a filled magnesium oxide cement with no clear demarcation between the roles of matrix and filler. occurs. The optimum length of the microfibers will, of course, vary in part depending on the thickness of the filled or foamed product being formed. For example, relatively thick panels can be manufactured using relatively long microfibers. The microfiber filler in the fully filled inorganic plastic cement is about 2% to about 40% of the inorganic plastic cement.
It should be present in amounts ranging over % by weight. The suitable amount of microfiber filler in the complete product is
It ranges from about 5 to 20%. A preferred microfiber is one made of glass. That is, the filler consists of short lengths of glass fibers. So-called "milled" glass fibers are particularly good because the milling process serves to separate the short glass fibers into discrete parts that can be properly oriented in the mineral plastic cement. Milling also gives some glass particles, but enough remains as individual fibers to accomplish the primary purpose of the microfiber filler. Microfibers are approximately 5 to 1500
can have an aspect ratio in the range of . Examples of suitable glass fiber fillers are those having a length of about 0.08 to 0.7 cm and a diameter of about 0.01 mm, giving an aspect ratio of about 100 to 850. The glass fibers used can be surface treated according to known methods that are fully explained in the literature (e.g. K. L. Lowenstein, “Methods for the manufacture of continuous glass fibers”, Elsevier Scientific Publishing. Inc., New York, 1973, pp. 191-233). However, the surface treatment of glass fibers
As is clear from the data in Table 1 below, this is not always necessary. Fibers other than glass fibers meeting the above specifications can also be used. Such fibers include, but are not limited to, those formed from mineral slag, asbestos, and the like. In producing the liquid molding composition of the present invention,
The reactive slurry is formulated as described above and shown in FIG. 1 and incorporated with the desired amount of microfiber filler. This can be done by adding the microfiber filler into the slurry tank and mixing at low speed, or by first transferring the slurry into another blender and then adding the microfibers. . It has been found that in some circumstances it is desirable to first disperse the microfibers in the slurry by high shear mixing prior to low speed mixing. The resulting slurry/filler composition is then transferred into a suitable mold for curing with or without heat and pressure. Reactive slurry/filler mixtures can also be used in lay-up or spray-up molding, filament winding, or pultrusion. The production of magnesium oxide cement from a reactive slurry is somewhat exothermic and when not cooled before adding the filler to produce a filled magnesium oxide cement, the heat of the exothermic reaction is
Can be used to increase cure strength.
Curing can also be carried out at room temperature or under heating up to about 125°C. Secondary fillers other than microfiber fillers,
It may be added in addition to the microfiber filler. Such secondary fillers include, for example, relatively long fibers of a wide range of materials such as glass, asbestos, mineral wool, synthetic resins in fiber or microform, and for example mica, talc, perlite, vermiculite, Also included are particulate fillers such as, but not limited to, polystyrene, Hezo, glass microballoons, and the like.
Some of these secondary fillers, such as relatively long fibers, can be added to provide improved strength to solid filled products, while others, such as perlite, vermiculite, polystyrene beads or glass Others, such as microballoons, can be added primarily to reduce the density of the final product. As shown in FIG. 1, it may be desirable to add at least some portion of such secondary filler along with the microfibers to the reactant slurry. by that the amount of any one secondary filler or combination of secondary fillers must have such a softness that the filled molding composition can assume the shape of the mold; be controlled. In the formation of solidly filled inorganic plastic cements, this means that it is possible, although not necessarily desirable, for the filled molding composition to even have a pasty consistency. Preferably, the filled molding composition is of such softness that it can be poured into a mold. The secondary fillers described above, as well as a preferred class of secondary fillers, glass fiber mats, can also be combined with the filled molding composition during the molding process.
Such glass mats, which are currently commercially available, are non-woven mats formed from either continuous or chopped strands (typically about 2 inches long). It can be of type or woven type. These mats typically have a weight of about 150 to 600 grams per square meter (about 1/2 to 2 ounces per square foot). When used as a secondary filler with fiberglass mats, the filled magnesium oxide cement compositions are formed into fiberglass laminates by any technique known for the production of laminates using organic resins. The curing cycle is 93.3~121.1℃ (200
~250°) in a matte tie for about 3-5 minutes, or for room temperature curing, for 24 hours or more. Addition of secondary fillers other than glass fiber mat during the molding process can be achieved by known methods such as hand lay-up or spray-up, reactive slurry/microfiber filling. The agent blend and secondary filler are fed through separate feeding means. Secondary fillers can be added to control the processing properties of the filled composition (ie, viscosity, thixotropy, etc.) as well as the physical properties of the final product. During the shaping step, one or more surfaces of the final product may be formed in the form of a layer of a plastic cement/filler mixture having a composition and/or proportions different from that of the main body of the solid-filled product. Sometimes it's desirable. As shown in Figure 1, this is suitable, for example, for forming the desired surface or surfaces of a molded article using some reactant slurry with only long fibers (secondary filler). This can be done by lining the cavity of the mold. For molded products, some form of surface finish,
For example, it may be desirable to apply a film or spray coating. This can be done by any suitable method. The examples described below are intended to be illustrative and not limiting of the products, compositions, and methods of the present invention as applied to the formation of solidly filled inorganic plastic cements. The reactant slurry used in the following examples was prepared by preparing a gauging solution containing 70% by weight of magnesium chloride heptahydrate.
formed. The gauging solution was prepared by adding the desired amount of water-soluble phosphorus oxide to 105.5 parts by weight of water,
It was prepared by adding 237.5 parts by weight of magnesium chloride hexahydrate to produce a highly concentrated (70%) solution. To this gauging solution, 282 parts by weight of magnesium oxide was then added using high shear mixing to form a reactant slurry. Finally, the microfiber filler was uniformly mixed into the reactant slurry. In preparing samples for measuring modulus of fracture and impact strength, the slurry/filler blend thus formed was deposited at a thickness of 0.318 cm or
Pressing or molding into one panel of 1.27 cm,
In some cases, these were heat-cured.
Test specimens were cut from these panels. Modulus of failure is measured using 2.54 cm x 15.24 cm specimens tested according to ASTM Test D-790;
The impact strength (Sharpy value) was measured according to ASTM test D-256 method B. In this latter test, a pendulum is used to strike the specimen,
Amount of energy required for destruction (m・Kg/cm ² ) (ft
- lb/in ² units). The effect of adding microfiber filler to magnesium oxide cement on modulus of fracture and impact strength is shown in Table 1. In Examples 2-7, these measurements are each an average of two tests. that the addition of microfiber fillers significantly increases the modulus of failure over that for unfilled magnesium oxide cement, and that these fillers increase impact strength by a factor of about 2-7; it is obvious.

[Table] One of the most important properties required for materials used to form various structures, such as bathroom vanities, is tensile strength. For measuring the tensile strength of the filled magnesium oxide cement of the present invention, a reactant slurry was prepared as described above using 2% by weight of phosphoric acid of magnesium oxide as the water-soluble phosphorus oxide component. To this slurry was then added 0.159 cm starched milled glass fibers at 8% by weight of the slurry. The resulting slurry/filler blend was then sprayed onto an acrylic sheet to form a vanity. A series of 1 inch (2.54 cm) square specimens were cut from this vanity and bonded between 1 inch (2.54 cm) square blocks of aluminum. ASTM Exam C297
Tensile strength was measured by pulling the block under tension until failure according to the method of . 8
The average values of several such measurements are given by way of example in Table 2.

[Table] In order to compare the tensile strength of the filled magnesium oxide cement of the present invention and the magnesium oxide cement containing only long glass fiber reinforcement material, the same vanity structure formed from acrylic sheet was prepared using a known spray The same reactant slurry and 2 inch (5.1 cm) chopped glass roping were sprayed by the up method. At this time, the reactant slurry and the glass fibers from the chopper were simultaneously but separately directed onto the acrylic sheet. The tensile strength of this reinforced magnesium oxide cement was measured in the same manner, and the results of the two measurements are shown in Table 2 as Examples 9 and 10. The average tensile strength of the magnesium oxide cement produced according to the present invention is approximately (42.2 Kg/cm ² )
(600 psi), whereas the value for the same inorganic cent reinforced with relatively long glass fibers is
On average (10.5Kg/cm ² ) (149psi). This represents a fourfold increase in tensile strength and a significant improvement in the properties of the microfiber-filled inorganic plastic cement. The data in Table 3 shows the use of a secondary filler (glass mat) in combination with a microfiber filler. The reactant slurry used for Examples 11-14 contained 2% phosphoric acid and 1% sodium hexametaphosphate by weight of magnesium oxide as the water-soluble phosphorus oxide component, whereas for Examples 15-14 Slurry No. 17 contains only 2% phosphoric acid. The test panels used for Examples 11-14 and 17 were prepared by placing a liquid composition consisting of a slurry/filler blend into a plate mold (43.3°C) (110°C) optionally containing a glass mat.
〓) It was thermoformed by being heated to 〓). The test panels used for Examples 15 and 16 were similarly prepared, ie, cold formed, without heating. The glass mat used was of the random non-woven continuous strand type.

【table】

Table 3 shows that when only glass mats were used (Examples 11 and 15), the modulus of failure was lower than when microfibers were added to the slurry. It is also important to note that the combination of microfiber fillers and secondary fillers has a synergistic effect on the modulus of failure of the combined fillers, as shown in Example 15.
And as shown in 17, pine only 767Kg/cm
(10900psi) and 0.159cm milled glass fiber only 162
Kg/cm ² (2310psi) to 929Kg/cm ²
(13210psi), which is greater than the total value of 999Kg/
cm ² (14200 psi) (Example 16). The reactant slurry blended as above is
It was finished using 2% by weight of phosphoric acid of magnesium oxide as a water-soluble component. This slurry has length
A predetermined amount of sprayed mineral fibers shorter than 6.4 mm (1/4 inch) in an amount equal to 40% by weight of the slurry;
added. The resulting slurry/filter blend was a hard rubber paste-like composition that could be calendered or pressed into the desired shape. The method of the invention as applied to the formation of foam-filled inorganic plastic cement is illustrated in FIG. This figure is by introducing a gaseous component into the slurry that is capable of foaming the slurry so as to bring it into a foamed form. Three types of foaming methods (indicated by , and) are shown.
The process is produced by decomposition or reaction in an alkaline environment and can be typified by the decomposition of hydrogen peroxide. Including the use of chemical blowing agents. The method uses a blowing agent that vaporizes under alkaline conditions and at a temperature below that at which the slurry solidifies. Blowing agents of this type can be exemplified by the use of fluorinated hydrocarbons. The method involves foaming by introducing an inert gas into the slurry to achieve mechanical foaming. As can be seen in FIG. 2, a gauging solution consisting of water, phosphorous oxide and magnesium salt is formed in the same manner as described above using the same solids concentration. The effect of relatively high magnesium salt concentrations in the gauging solution on the density, tensile strength and cell structure of the foamed product is shown in Table 4. The data in Table 4 shows relatively high magnesium salt concentrations (Example
21-24) are necessary for obtaining a good foamed product.

[Table] In formulating the composition to obtain the data in Table 4, the slurry was mixed with 1:5 _MgCl2 .
_6H2O :MgO molar ratio, which also contains 4% hydrogen peroxide (30% concentration) by weight of the slurry;
It contained 0.005% KMnO ₄ , 2% zinc stearate as a surfactant and 16% 0.635 cm bonded milled glass fibers. The foam was cured under ambient conditions. As mentioned above, the first foaming method shown in FIG. 2 uses a foaming agent generated by decomposition, such as the decomposition of hydrogen peroxide. It is generally preferred to incorporate a hydrogen peroxide decomposition catalyst into the filled foamable composition thus formed. If a decomposition catalyst for hydrogen peroxide is used, it can be added to the slurry in the form of a concentrated aqueous solution and thoroughly mixed. Alternatively, it may be added as a solid to the water used to prepare the gauging solution prior to addition of the magnesium salt. If a hydrogen peroxide-free composition is to be stored for a period of time, it is desirable to add the catalyst as an aqueous solution immediately before adding the hydrogen peroxide. The use of such decomposition catalysts has a significant effect on the rapidity of bubble formation.
And more importantly, it exerts some control over the density and cell structure uniformity of the final product. Generally, the use of hydrogen peroxide decomposition catalysts is
Increases the rate at which decomposition occurs and therefore the rate of foaming. On the other hand, it produces relatively low density and tensile strength, as well as relatively small cell size. This can be seen by the examples (25-27) in Table 5. In formulating the compositions to give the foamed products of the Examples in Table 5, 70%
using a gauging solution of MgCl ₂ 6H ₂ O, and
The molar ratio of MgCl ₂ .6H ₂ O:MgO was 1:5. The slurry contained 1% by weight sodium hexametaphosphate 5% by weight 0.635 cm milled glass fibers and 3% by weight calcium or sodium stearate as a surfactant. Hydrogen peroxide was added as a 30% aqueous solution.

[Table] The data in Table 5 show that the use of a relatively small amount of hydrogen peroxide and a relatively large amount of permanganate (Example 28) resulted in good density, a significant increase in tensile strength and a fine It has also been shown that foamed products with cellular structures can be provided. Thus, by varying the amount of hydrogen peroxide decomposition catalyst and its weight ratio to the hydrogen peroxide used,
Control over the density, tensile strength and cell structure of the final product is possible. Any compound known to promote the decomposition of hydrogen peroxide (e.g., compounds containing iron, cobalt, manganese, nickel, etc.) can be used and is added to about 0.5 of the slurry weight.
It can be added in amounts up to %. The preferred catalyst for this is potassium permanganate. In forming filled foam compositions with desirable properties, it is necessary to use what can be termed "emulsifying" surfactants. The surfactant serves to provide some control over the cell structure and size, as well as density, of the foamed product. The surfactant is added to an aqueous slurry consisting of phosphorous oxide, magnesium salt, and magnesium oxide.
The addition of the surfactant is such as to ensure uniform dispersion of the surfactant throughout the slurry.
I have to do it. Preferably, this is done in a high shear mixing device. The surfactant must be water repellent and anionic. Such suitable surfactants include oleic acid, stearic acid, salts of stearic acid such as ammonium stearate, sodium, magnesium, zinc and calcium, anionic silicone resin emulsions, mixtures thereof, etc. However, it is not limited to these. A number of compositions were formulated using various anionic water repellent surfactants with different amounts of hydrogen peroxide, decomposition catalyst, and reinforcing filler materials. The basic composition used was 70% gauging solution, _MgCl2 .
It consisted of a 1:5 molar ratio of 6H ₂ O:MgO and 1% by weight of the slurry sodium hexametaphosphate. The foam was allowed to cure under ambient conditions. The density and tensile strength of the foamed products produced are shown in Table 6. The foams having the compositions in Table 6 all had acceptably fine cell structures.

TABLE The influence of the presence of surfactants on the properties of the foamed product is further illustrated in the examples in Table 7. Besides using 0.005% KMnO ₄ , 4% H ₂ O ₂ (concentration 30%) and 16% filler based on the weight of the slurry.
The same basic slurry was used as in the examples shown in Table 6. Zinc stearate was used as a surfactant in varying amounts.

TABLES From the data in Tables 6 and 7 it can be seen that at least about 1% of surfactant by weight of the slurry is required to provide a fine cell structure. However, if a relatively less homogeneous cell structure is acceptable, for example in some types of insulators, the weight of the slurry may be reduced.
Amounts of surfactant as low as 0.5% can be used. As is evident from the examples in Tables 6 and 7, increasing the amount of surfactant from 2% to 3% appears to result in a slight increase in density and tensile strength. However, although it is possible to add more than 3% by weight of surfactant, the use of significantly more than about 3% does not result in any significant effects as far as the properties of the foamed product are concerned. You can't even make a profit. In some cases, the transfer of blowing agent molecules from solution in the slurry to the gas phase is achieved by adding a small amount, e.g., up to about 0.5% of the weight of the slurry, of a nucleating agent, e.g., silicone oil. Sometimes it is desirable to help. If the anionic surfactant itself is a silicone resin emulsion, there is no need to add a separate nucleating agent. If a nucleating agent is used, approximately 0.5% of the weight of the slurry, with or after the addition of surfactant to the slurry.
Add in an amount up to . The aqueous slurry thus formed containing water-soluble phosphorus oxide, magnesium salt, magnesium oxide, surfactant, hydrogen peroxide decomposition catalyst, and, if used, nucleating agent, contains about
It should have a viscosity in the range of 700 to 15,000 centipoise, with a preferred range being about 700 to 2,500 centipoise. The reactant slurry at this stage, prior to the addition of the blowing agent, is preferably non-thixotropic, especially if it is desired to obtain the lowest density in the final product. Once a slurry of the desired viscosity has been produced and thoroughly mixed, the slurry is ready for the addition of filler material. In addition to microfibers, secondary fillers can also be used, such as those mentioned above. The microfibers and any secondary fillers added prior to shaping are incorporated into the reactant slurry prior to the addition of hydrogen peroxide, as in the manufacture of solid products. The viscosity of the final foamed composition (filled reactant slurry) is:
It can be up to about 100,000 centipoise, but a range of 2,000 to 25,000 centipoise is preferred. The amount of filler material that can be added is related to the nature of the material. In general, if only microfibers are added, and if the microfibers are of relatively short length and can be wetted quickly so that they are easily dispersed throughout the foam structure, It is possible to add a larger amount than in the case of a material that is large and difficult to disperse. This is shown in the data in Table 8. In formulating the foam compositions for the examples in Table 8, a 70% gauging solution was used, and the slurry prepared thereby was 1: ₅ MgCl2.
It had a molar ratio of 6H ₂ O:MgO. To this slurry, 1% by weight of sodium hexametaphosphate, 2% by weight of stearate (zinc or ammonium), 4% by weight of H ₂ O ₂ at a concentration of 30%;
KMnO ₄ (0.005% by weight for Examples 38-58,
0.007% by weight for Examples 59-61) and organosilicone (0.5% by weight for Examples 38-58 and 0.1% by weight for Examples 59-61). To this base composition various glass and mineral fibers were used as microfiber fillers and glass microfibers were added as secondary fillers. Density and tensile strength were measured on the final foamed products cured at room temperature. From the data in Table 8, it can be seen that when milled glass fibers are used as the reinforcing filler material (Examples 39-55), a larger amount of filler is added than when chopped fibers are added (Examples 56-58). It is clear that it is possible to use This difference is due to the easier dispersion of the filler due to the separation of the fibers during milling. Additionally, water-binding fibers treated to bind water-based materials (Examples 39-
46) can be used in higher amounts than starch-bound (Examples 50-55) or cationic surfactant-treated (Examples 47-49) milled fibers. In the case of starch-bound fibers, the starch coating on the fibers contributes to the viscosity of the foamed composition, and this starch increases the viscosity of the foamed composition to the point where foaming and subsequent processing becomes difficult. , it is thought that it will reach an increasing level.

【table】

Table 1 Thus, the amount of inorganic reinforcing filler material added depends on the nature of the filler material and the desired tensile strength. The maximum amount of filler material used is no greater than an amount that increases the viscosity of the filled foam composition to about 100,000 centipoise and less than an amount that causes foam collapse. The optimum amount of filler material within these ranges is that amount necessary to obtain the desired tensile strength within a given density range. Filler up to about 25% of the weight of the slurry can be added as long as the above requirements are met. In selecting the filler material, it is desirable that the bulk (greater than 50%) of the filler used be microfibers; fibers spanning a length of about 0.08 to 0.7 cm are preferred. Generally, the smaller the size of the filler, the greater the ability to incorporate it and still provide a foamed composition that is capable of curing into the desired structure. It goes without saying that along with the microfibers, one or more secondary fillers may be present, which can be longer inorganic or synthetic organic resin fibers, finely particulate materials and/or mixtures of these fillers. Combinations are also within the scope of this invention. As seen in FIG. 2, the hydrogen peroxide blowing agent is added to the charged reactant slurry by thoroughly mixing it throughout the slurry. Addition of hydrogen peroxide is carried out to the slurry under ambient conditions. The decomposition of hydrogen peroxide into water and oxygen is
Needless to say, it is exothermic. The hydrogen peroxide blowing agent is preferably used in the form of an aqueous solution, which can have a relatively wide concentration range. The preferred concentration is about 30% because it is commercially available and is a stable form of hydrogen peroxide. The amount of hydrogen peroxide used has a direct relationship to the density and tensile strength of the final product, as shown in the Examples in Table 9. In formulating these compositions for foaming, a 70% gauging solution of MgCl ₂ .6H ₂ O was used and the molar ratio of MgCl ₂ .6H ₂ O:MgO was 1:5. Slurry is 0.318cm of 1% by weight
It contained milled glass fibers, 2% by weight zinc stearate and 0.1% by weight silicone resin emulsifier. The foamed product was cured under ambient conditions.

【table】

TABLE The data for the examples in Table 9 show that for any one system, increasing the amount of hydrogen peroxide decreases the density and tensile strength of the foamed product. The amount of hydrogen peroxide at a concentration of 30% is approximately 0.08
It can range from about 0.25% to about 8% of the slurry weight to obtain a density range of 5 to 100 lb/ ^{ft 3 .} This range for hydrogen peroxide is for convenience only 100%, since aqueous hydrogen peroxide solutions with concentrations other than 30% can be used.
Expressed on a hydrogen peroxide basis, this amounts to about 0.075% to about 0.25% by weight of the slurry. Other blowing agents that can be used in place of hydrogen peroxide include, but are not limited to, toluene-(4-sulfonylhydrazide) and 4-4'-oxybis(benzenesulfonylhydrazide). . Such blowing agents must be capable of generating the required amount of gaseous product at temperatures not higher than about 125° C. in an alkaline environment. Once the filled foam composition has been formed, it can be poured into any suitable mold for expansion into a foamed state and for final gelling, solidification and curing. The mold surface may be coated with a suitable release coating, such as a fluoropolymer, silicone oil or wax.
It may be coated. The shaping of filled foam compositions is similar to that described for the shaping of solid products; and the same class of secondary fillers can be added during the shaping step. Similarly, the filled foam compositions can be formed into laminates with glass fiber mats; and the resulting foam-filled mineral reinforced plastic cement products may contain one or more fillers (microfibers and/or molding having one or more surfaces of solid, filled plastic cement by coating said surfaces of the mold with an unfoamed or non-foamed reactant slurry containing a secondary filler. You can also. Thus, the finished product can be a structure with a foamed core and one or more filled solid layers on its surface. It is also possible to carry out a surface finishing of the foamed product produced. Although the foam can be cured at room temperature for an extended period of time, such as several days, in industrial practice it is preferred to cure using heat. Heat can be supplied in the form of infrared radiation, a hot platen or a hot gas such as water vapor, air, etc. The temperature at which curing is carried out is one that finishes the foamed structure to a temperature no higher than about 125°C. An example of heat curing is keeping the mold with the foamed composition in a heated air oven at 95°C, 125°C or 155°C;
inch) to a remote infrared radiation source for 15 minutes and heating the foam panel in a hot platen press or steam chamber for 15 minutes at 105°C or 13-15 minutes at 120°C. It is thus clear from these examples that a wide range of thermal curing is possible. Table 10 shows typical densities and tensile strengths for oven curing at three different temperatures. The foam composition for the examples in Table 10 was 1:5 MgCl ₂ at 70% by weight of the slurry.
gauging solution with a molar ratio of _6H2O :MgO,
Prepared using a slurry consisting of 4% (30% concentration) hydrogen peroxide, 1% sodium hexametaphosphate, 0.005% KMnO ₄ , 2% zinc stearate, and 16% water-bonded milled glass fibers. .

[Table] All of the above examples were formulated using magnesium chloride, MgCl ₂ 6H ₂ O, as the magnesium salt.
It will be apparent that magnesium sulfate, MgSO ₄ .7H ₂ O, can be used in forming the foamed inorganic resins of the present invention. This is the 11th
Illustrated by the examples in the table. In both of these examples, the water-soluble phosphorus oxide is 1% sodium hexametaphosphate, the hydrogen peroxide decomposition catalyst is 0.005% _KMnO4 , the surfactant is 2% zinc stearate, and the loading The agent is 6% 0.635
cm water bonded milled glass fiber and blowing agent is 4
% (concentration 30%) of H ₂ O ₂ . All of these percentages are based on the weight of the slurry.

A second method that can be used to form a filled foam composition is vaporization in an alkaline environment of the slurry at temperatures below about 120°C. Including the use of blowing agents. Examples of such blowing agents are fluorinated hydrocarbons and hydrocarbons such as, for example, pentane, hexane or heptane. In applications requiring essentially complete naturalness, fluorinated hydrocarbons are preferred. The following description of the second foaming method refers to the use of fluorinated hydrocarbons as the blowing agent. As is clear from Figure 2, the gauging solution is
Produced in a similar manner using the same solids concentrations for phosphorus oxides and magnesium salts as used for the enriched product (Figure 1) and the foamed product using hydrogen peroxide blowing agent. . The concentration of magnesium salt in the gauging solution affects the cell size and uniformity in the final foamed product. That is, as in the case of using hydrogen peroxide as a blowing agent (see Table 4), as the magnesium salt concentration increases, the size of the bubbles decreases and the degree of uniformity increases. In forming the reactant slurry, magnesium oxide is incorporated into the gauging solution by high speed, high shear mixing, as in forming the enriched product. The same range of molar ratios of magnesium salt:magnesium oxide is used. Also during high speed, high shear mixing, an "emulsifying" (water repellent, anionic) surfactant is added in an amount ranging from 0.5 to 3% of the total slurry weight. Finally, a nucleating agent may be added, similar to when hydrogen peroxide is used. The aqueous slurry thus formed containing water-soluble phosphoric oxide, magnesium salt, magnesium oxide, surfactant, and, if used, nucleating agent, has a viscosity in the range of about 700 to 15,000 centipoise. The preferred range is about 700 to 2500 centipoise. The slurry at this stage, prior to the addition of the blowing agent, is preferably non-thixotropic, especially if one desires to obtain the lowest density in the final product. Once a slurry having the desired viscosity has been formed and has been thoroughly mixed, it may be necessary to adjust the temperature of the slurry prior to adding the blowing agent. The temperature of the slurry should be at least a few degrees (eg, about 2-3°C) below the boiling point of the blowing agent. This allows sufficient dispersion of the blowing agent as a liquid throughout the slurry before an appreciable increase in volume occurs. Suitable blowing agents are liquid fluorinated hydrocarbons having a boiling point below the curing temperature of the foam. The blowing agent can be added to the slurry without requiring extensive cooling of the slurry, while at the same time achieving foam hardening at temperatures only slightly above room temperature, if desired. In order to make this possible, it is preferable that the boiling point is several degrees higher than room temperature. Under normal conditions, the slurry after mixing is complete will be several degrees above 21° C. (room temperature). If it is then cooled to 20° C., a fluorinated hydrocarbon such as CCl ₃ F (boiling point 23.8° C.) can be added. To ensure the generation of bubbles with uniform size,
It is important that the blowing agent is thoroughly and uniformly mixed into the slurry. As the mixture is thoroughly mixed to disperse the blowing agent, the temperature increases to the point where the blowing agent reaches its boiling point, resulting in the formation of bubbles, and subsequent bubble growth causes a significant increase in volume. bring. Needless to say, it is desirable that such volume increase occur primarily within the shape of the mold. When the foamed composition is prepared as described above, the foamed slurry does not gel before it reaches the point of maximum volume increase. Moreover, the foam has sufficient green strength stability so that it does not collapse before the plastic cement is allowed to set and harden. The performance characteristics of such foams are, of course, absolutely necessary, and they are unique in the methods and compositions of the present invention. The final foam density is primarily controlled by the amount of blowing agent added. However, the surfactant used, the viscosity of the slurry and the ratio of magnesium salt to magnesium oxide in the gauging solution as well as the solids concentration and degree of dispersion of the blowing agent also have some influence on the density of the resulting expanded inorganic plastic cement. affect The microfibers, along with optional secondary fibers, can be added immediately before, simultaneously with, or immediately after the addition of the blowing agent. The viscosity of the final filler foam composition can be up to about 100,000 centipoise, with a range of 2,000 to 25,000 centipoise being preferred. The final molding composition is
It doesn't have to be a trivial thing. Added fillers are the microfibers described above and optional secondary fillers that may be desirable to impart increased strength, reduced density, and other physical properties. The amount of such filler is the same as that desired for foamed products made by using hydrogen peroxide as a blowing agent. The effect of the addition of microfibers on the density and tensile strength of foamed products using hydrocarbon blowing agents is shown by the data in Table 12. In obtaining these data in Table 12, the molar ratio of _MgCl2.6H2O : _MgO was 1:5, the gauging solution concentration was 70%, and 1% by weight of water-soluble phosphate was used. Adding sodium hexametaphosphate, using 2% by weight ammonium stearate as a surfactant and as a nucleating agent.
0.5% by weight silicone oil was added to form a reactant slurry. The blowing agent was _CCl3F . The basic reactant slurry had a viscosity of about 700-2500 centipoise. The tensile strength of the expanded inorganic plastic cement was measured by the method of ASTM D638.

[Table] As with the use of hydrogen peroxide as a blowing agent, it is desirable that the major portion (greater than 50%) of the filler be microfiber filler. about
Fibers ranging in length from 0.8 mm to 0.635 cm are preferred. Generally, the smaller the size of the filler, the greater the ability to add it and still obtain a foamed composition that can solidify into the desired structure. The amount of filler material added will thus depend on the nature of the filler material and the desired tensile strength. The maximum amount of filler material used is no more than an amount that increases the viscosity of the foam composition to about 100,000 centipoise and less than an amount that causes foam collapse. The optimum amount of filler material within such range is that amount necessary to obtain the desired tensile strength.
Generally, about 20% filler by slurry weight is the maximum amount for the foamed material. Once a filled foam composition is produced, it is subjected to final gelling, solidification and curing.
It can be poured into a suitable mold. The surface of the mold is
It can be coated with a suitable release coating such as, for example, a fluorinated polymer, silicone oil or wax. Including glass fiber pine,
The secondary filler is added during the molding step as before.
and may be formed as a solid, unfilled inorganic plastic cement coating on one or more surfaces of the foam product. In industrial practice, it is usually desirable to achieve curing by heating. Heat can be provided in the form of infrared radiation, hot gases such as air, water vapor, etc. The temperature at which this curing is carried out must be such that it does not raise the temperature of the foamed product above about 125°C. During curing of either solid or foamed products, the temperature of the inorganic plastic cement must be kept below a level at which appreciable dehydration of the cement occurs. Finally, filled foam compositions suitable for forming the foamed products of the present invention include inert gas in which the reactant slurry can be vigorously agitated or whisked to produce the desired degree of expansion. By introducing this, it is possible to have the machine form it. As illustrated in FIG. 2, a reactant slurry containing a water-repellent anionic surfactant and, if used, a nucleating agent, can be foamed by one of two methods. In the first method, the reactant slurry is bubbled in air at atmospheric pressure or, ^e.g.
(100-200 psi) and bubbled with an inert gas such as air, nitrogen, argon, etc. and then expanded to atmospheric pressure. In the second method, water containing a surfactant is used to form a separate foam, and this preformed foam is incorporated into the reactant slurry. In this case, the concentrations of magnesium salt and magnesium oxide in the reactant slurry are relatively high within the ranges specified above, such that the addition of water in the preformed foam increases their concentration. It is preferred not to reduce the concentration of the magnesium compound below a level at which the cell size and uniformity are no longer acceptable (see, for example, Table 4). If a reactant slurry is generated,
Microfiber fillers and optional secondary fillers can be incorporated to provide filled foam compositions. Alternatively, as seen in FIG. 2, the microfiber filler and any secondary filler materials are added to the reactant slurry and the foaming of the fill composition is carried out by one of the two methods described above. It can also be carried out either by whisking or by incorporating preformed foams. The thus formed filled foam composition may be placed in a mold and a secondary filler may be added, or the filled foam may be laminated with a glass fiber mat. In molding, one or more surfaces can be formed from unfilled solid inorganic plastic cement as described above, and the foamed solid inorganic plastic cement product can also be surface-finished as described above. . From the above examples, it can be seen that the addition of multidirectionally oriented microfiber fillers throughout the inorganic plastic cement in solid or expanded form
It is clear that there is a significant contribution to the physical properties of this type of material. Of particular importance is the significant increase in tensile strength that can be achieved when using microfiber fillers and when microfiber fibers are used in combination with secondary fillers, such as glass matte. This is a synergistic effect (see Table 3). In the latter case, the microfiber filler is believed to be able to transfer stress within the cement matrix such that the loads on the magnesium oxide cement are transferred to the secondary filler, which acts as a reinforcing agent. . It is thus believed that this mechanism allows inorganic plastic cements to be effectively reinforced and utilized for many applications not possible using conventional unfilled materials. The foamed products of the invention are notable and distinctive due to their physical properties. A cell structure is a structure in which the uniformity of cell size throughout a foam is at least partially dependent on the cell size, with the degree of uniformity increasing as the cell size decreases. do. In structures where the cell size can be classified as large (e.g. having a diameter greater than 3 mm), non-uniformity in cell size may be a problem in some applications, especially when foam structures are subjected to significant loads. Applications that must carry
on the other hand, are sufficiently significant to render such structures generally unacceptable. The diameter of the bubble is approximately 1.25 to 3 mm (the cross-sectional area is approximately 1 to 7 mm ² )
For structures in the range of , the bubble size is substantially uniform; and fine (1.25 mm diameter).
In structures with cells classified as small (with a cross-sectional area of about 1 mm ² or less), the cells are essentially all homogeneous. Preferably, essentially all the cells have a cross-sectional area of about 2 mm ² or less. In a preferred embodiment of the foamed product of the present invention,
A portion of the cells, such as at least about 5%, are closed cells and contain moisture trapped therein. Because some of the blowing agents used have low heat transfer coefficients, foam compositions containing such blowing agents and having a large proportion of closed cells can be excellent thermal insulators. Become. The density of foamed products ranges from about 5 per cubic foot to about
It can range from 100 pounds (0.08 to 1.6 g/cm ² ). The preferred density range is approximately per cubic foot.
15 to 50 pounds (0.24 to 0.8 g/cm ³ ). As mentioned above, the tensile strength can be controlled and varied from essentially zero values for supporting insulation to values as high as 100 pounds per square inch (7 Kg/cm ² ) or more. I can do it. The end use of the foamed product will, of course, specify the desired strength. The reactions to form these inorganic plastic cements consume essentially all of the hydration water and essentially all of the water added to form the slurry, so micro The total amount of fiber and secondary filler can range up to about 40% of the finished cured solid product and up to about 25% of the finished cured foam product. Finally, filled and foamed products are water resistant and non-hygroscopic. They are non-flammable and exhibit essentially zero flame spread, zero smoke density, and zero fuel contribution. For example, Enden has tested and determined that the performance of its foam products is comparable to that of asbestos, which has a rating of zero; and has a critical oxygen index greater than 95. The method of the invention thus provides a new product which has unique properties and is particularly suitable for construction purposes. Give the product a wide range of uses. A wide range of densities, tensile strengths and other physical properties can be achieved. It is clear from the foregoing that the said objects of the invention are efficiently achieved and that certain modifications may be made to the method carried out and to the product described without departing from the scope of the invention. It will also be clear that all matters contained in the above description are set forth by way of example and not in a limiting sense.

[Brief explanation of the drawing]

FIG. 1 is a flow diagram of the process of the present invention showing the formation of a solid morphology inorganic plastic cement. Second
The figure is a flow diagram of the method of the invention showing the formation of a filled inorganic plastic cement in foamed form.

Claims (1)

[Claims] 1 (a) Consists of a magnesium salt, a water-soluble phosphorus oxide component and magnesium oxide, and has a molecular weight of about 700 to 15,000
forming a reactive aqueous slurry having a viscosity in the centipoise range; (b) adding microfiber filler into the aqueous slurry, prior to solidification, in an amount of 2% to 40% by weight of the slurry; 1. A method for producing a filled inorganic plastic cement, comprising the steps of: mixing fiber fillers non-planarly and multidirectionally in the resulting filled inorganic plastic cement composition. 2. The magnesium salt is magnesium chloride hexahydrate, and the molar ratio of the magnesium chloride hexahydrate to the magnesium oxide is 1:3 to 1:9.
or the magnesium salt is magnesium sulfate heptahydrate;
The molar ratio of heptahydrate to the magnesium oxide is 1:3
The method of claim 1, wherein the ratio is 1:14 to 1:14. 3. The reactive aqueous slurry does not contain an appreciable excess of water over the amount of water required to form the plastic cement.
The method described in section. 4. Claims 1 to 3, wherein the water-soluble phosphorus oxide component is a glassy phosphate, phosphoric acid or a mixture thereof present in the slurry in an amount up to 6% by weight of the magnesium oxide. The method described in any of the paragraphs. 5. The method of claim 1, wherein the microfiber filler consists essentially entirely of short fibers of a length that allows them to be oriented in multiple directions in the filled inorganic plastic cement. 6. The method of claim 1, wherein the amount of microfiber fibers is between 5 and 20% of the weight of the slurry. 7. The method of claim 1 further comprising the step of also adding a secondary filler into the water slurry along with the microfiber filler. 8. The secondary filler comprises fibers longer than the microfiber filler, particulate materials, materials capable of reducing the density of the formed filled inorganic plastic cement, or mixtures thereof. The method described in Section 7. 9. The method of claim 1, comprising the step of shaping the filled inorganic plastic cement composition into a desired shape. 10. The method of claim 9, further comprising the step of adding a secondary filler during the step of forming the shape. 11. The secondary filler comprises fibers of longer length than the microfiber filler, particulate materials, fillers capable of reducing the density of the filled inorganic plastic cement formed, or mixtures thereof. The method according to scope item 10. 12. The method of claim 11, wherein the step of adding the secondary filler comprises laying up or spraying the secondary filler and the filled inorganic plastic cement composition. 13. The secondary filler comprises glass mat, and the step for adding the secondary filler comprises adding the mat with the filled inorganic plastic cement composition.
11. The method of claim 10, comprising impregnating under pressure and at a temperature of about 95 DEG to 125 DEG C. to form a laminate. 14. The method of any of claims 1-13, further comprising the step of curing the filled inorganic plastic cement composition under heating up to about 125°C. 15. On at least one surface of the filled inorganic plastic cement shape, a layer of filled inorganic plastic cement having a different filler combination and/or filler composition than the filled inorganic plastic cement forming the shape. 15. A method according to any of claims 9 to 14, comprising the step of forming. 16 introducing into the water slurry a gaseous component capable of expanding the slurry, thereby solidifying the slurry in a foamed form;
The step for introducing the gaseous component is prior to mixing the microfiber filler into the water slurry;
The method according to any one of claims 1 to 15, which is carried out simultaneously with or after mixing. 17. The method of claim 16, wherein the amount of microfiber filler is 2-20% of the slurry weight. 18 Claim 1 includes the step of adding a water-repellent anionic surfactant to the water slurry.
The method described in Section 6. 19. The method of claim 16, comprising the step of adding a nucleating agent to the water slurry. 20. A method according to any of claims 16 to 19, wherein the gaseous component is formed in the water slurry by reaction or decomposition of a chemical blowing agent. 21. The method of claim 20, wherein the chemical blowing agent is hydrogen peroxide and the water slurry contains a catalyst for decomposition of the hydrogen peroxide. 22. The gaseous component of claims 16-19, wherein the gaseous component is a vaporizable blowing agent that is inert in an alkaline environment and has a boiling point below the temperature at which the slurry solidifies in the foamed form. Any method described. 23. The method of claim 22, wherein the blowing agent is a fluorinated hydrocarbon having a boiling point slightly above room temperature. 24. The method according to any one of claims 16 to 19, wherein the gaseous component is an inert gas introduced into the water slurry under normal pressure or increased pressure. 25. The method of claim 24, wherein the gaseous component is introduced into the water slurry either directly or indirectly in the form of a preformed foam.