FI72307B - FORMAT FOEREMAOL SAMT FOERFARANDE FOER FRAMSTAELLNING AV DETSAMMA - Google Patents

Description

72307

Shape and composite material and method of making the same

General principles

Compact systems containing homogeneously arranged ultra-fine particles, briefly referred to as DSP in the following description and claims, are described in detail and defined for the first time in International Patent Application No. PCT / DK79 / 00047. The present invention relates to important further developments of DSP systems, e.g. new types of DSP systems and materials from the previously described DSP systems, new technology for providing DSP systems, and new uses for DSP systems.

DSP systems provide hitherto unattainable mechanical properties, e.g. strength, sealing, and durability in materials and articles based on these systems, and enable such articles and materials to be fabricated by inexpensive, hitherto unknown methods that expand the possibilities of providing advanced microstructures to structural materials with a wide variety of uses.

Briefly, the basic principles of DSP systems include arranging very finely divided particles or particles ranging in size from about 50 Å to about 0.5 microns into interstitially substantially tightly packed particles, i.e., particles with a particle size of about 0.5 microns. - about 100 μm, and which are at least as large as (') -10 larger in size than the very fine particles in question. Some important features of DSP systems are included in the following five sections: 2 72307 1. DSP systems apply known geometrical and kinematic principles to the mutual arrangement of bodies, especially particles, in the desired formation - especially very tightly arranged - in systems of fine particles or bodies of the order of 1-2 times finer than those systems where it has previously been possible to utilize this known particle geometry. DSP systems overcome the problems associated with the locking surface forces of adjacent bodies that have hitherto prevented colloidal sized bodies or particles from being arranged in the desired compact formation.

2. Despite the fine particles or particles of DSP systems, DSP material can be formed in a substantially low voltage range. This is possible by using the dispersants developed (for example, in a cement system with large amounts of concrete power softeners (1-4% by weight), which are as much as an order of magnitude larger than those used in the prior art.

3. DSP materials have substantially improved strength as well as durability. In addition to this, the mechanical fastening of the reinforcing bodies, for example the incorporated fine fibers, has been added more than the strength, this addition being of one or more orders of magnitude. This is due to the fact that the magnitude of the roughness and waveform of the reinforcing elements, which is necessary for the mechanical attachment of the reinforcing elements to the matrix, has been reduced by orders of magnitude of 1-2. This opens up the possibility of mechanically fastening fibers that are 1-2 orders of magnitude smaller than the fibers that have enabled fastening so far.

4. The quality (primary strength and stiffness) of the DSP materials of the invention can be further improved by the addition of other very strong particles (e.g. sand or stone of refractory bauxite to be added to Portland).

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3 72307 for cement-based DSP materials).

5. Typical DSP materials are materials that can be transformed from a plastic mass to a low viscosity mass by simple deformation without altering the environmental materials, which means that no liquid is removed or extruded from the mass to provide this compact structure. This makes it possible to produce products with high quality and a much more complex shape and size than before - and also makes it possible to attach components, especially all kinds of reinforcing elements, which cannot be satisfactorily (or not at all) used in corresponding high-quality conventional matrices. This property of DSP materials also opens up the possibility of new and more cost-effective manufacturing methods for known objects.

In this context, the terms "bodies" and "particles" refer to objects that have physical boundaries, while the term "physical" refers to specific properties, such as mechanical, electrical, optical, and chemical properties.

DSP Matrix Structure Shaped bodies containing a DSP matrix can be generally defined as shaped bodies comprising a unitary matrix in which the matrix consists of A) homogeneously arranged bodies or particles having a size of about 50 Å to about 0.5 μm, or a unitary structure that formed in this way from homogeneously arranged bodies or particles, and B) tightly arranged bodies or particles having a size of about 0.5 to 100 μm and at least on the order of size larger than the particles mentioned in A), or from such tightly arranged bodies or particles. a unitary structure of particles, 4 72307 wherein the particles A or the unitary structure formed therefrom is homogeneously distributed in the interstices of the particles B, and wherein this tight package substantially corresponds to a package obtained by mechanically gently acting on geometrically uniform large bodies or par a system of particles in which the effect of the clamping surface forces is substantially negligible, and an interparticle substance between the bodies or particles A and B or between the structures formed from these bodies or particles A and B.

The bodies or particles A and B are typically solid bodies or particles, but they can also be bodies or particles in the gas phase or in the liquid phase. Similarly, the interparticle substance may be solid, or it may be a substance in the gas phase or liquid phase, provided that when the interparticle substance in the formed DSP body is not solid, the necessary "adhesion" is provided to maintain the body by particle-particle bonding.

The substantially uniform structure of the matrix of DSP bodies as defined above is thus due to the fact that the homogeneously arranged or tightly packed bodies or particles A are joined together to form a uniform structure, or the above-mentioned solid particles B are joined together to form a substantially uniform structure, or that both very fine particles A and the particles B are joined together in a shaped body to form a uniform structure, and / or that the particles A and the particles B are combined into a uniform structure. In systems comprising cement particles as particles B and silica dust particles (as defined below) as particles A, the formation of a uniform structure results from the partial dissolution of solid particles in the aqueous suspension from which the bodies are formed, and the chemical reaction in solution. less reactive than cement. In this context, it should be noted that depending on the nature of the particles A and B, other mechanisms that cause attachment may also provide a uniform structure of the matrix, such as melting, sintering, etc. The above chemical reaction may occur between particles A or these dissolved bodies or particles B or between dissolved bodies, or between particles A and B or bodies formed from particles A and particles B.

A substantially uniform structure can also be obtained by solidifying another intermediate substance of the particles, for example by physically solidifying a melt or liquid, e.g. metal or glass melt, and by chemical solidification, such as polymerization, for example to form a plastic material.

Moldings containing a matrix having a substantially uniform structure, including homogeneously arranged or tightly packed particles A together with tightly packed Portland cement particles, could only be made in the prior art by compression in a high stress region, typically by high pressure powder compression. Thus, a very interesting group of shaped DSP bodies comprises shaped bodies made by molding in the low stress region 2, less than 5 kg / cm, preferably less than 2 100 g / cm, and having a matrix of substantially uniform structure containing homogeneously arranged or tightly packed particles A, or a unitary structure formed from such homogeneously arranged or tightly packed particles A, and 6 72307 tightly packed particles B, wherein at least 20% by weight of the tightly packed particles B comprise Portland cement particles, or a unitary structure comprising formed from such tightly packed particles B. Another way to define the group of shaped DSP bodies with homogeneously arranged particles A in the presence of tightly packed particles B, of which at least 20% by weight is Portland cement particles leita, is to refer to the dimensions of the paragraph. Pieces with a corresponding tight fit between the particles B and at least one dimension comprising at least 1 m and at least 2 0.1 m in cross section are not assumed to have been made in practice by high-pressure powder compression technology before the invention of DSP systems. Another way to describe DSP bodies of this type is by definition that the body has a complex shape that does not allow it to be made by powder compression. When particles b have a different molecular structure from particles A, which is often the case in practice, structures containing at least 20% by weight of particles B are Portland cement and which otherwise meet the above definition could not be prepared using conventional techniques regardless of their size. or form. Although the powder compression technique has made it possible to provide a combination of the two systems comprising homogeneously arranged or tightly packed particles A and tightly packed particles B, this has resulted in larger particles breaking up in the compression process into smaller particles and thus has meant that identical molecular structure.

One very interesting feature of DSP materials is that it is possible to provide structures of the above type with inherently weak particles and inherently weak attachments that would lose their geometric shape (break or experience appreciable deformation) by high tension in the prior art. This makes it possible to provide a dense structure with materials that have not previously been able to be used for this purpose.

In most cases, the most valuable strength properties can be achieved when both particles A and particles B are very tightly packed. This situation is illustrated in Figure 1 of International Application No. PCT / DK79 / 00047, which shows the principles of a geometric system comprising a fresh DSP paste consisting of a Portland cement particle closely matched to very fine particles between the Portland cement particles. In experiments with mortar, fiber-reinforced paste, and concrete based on this new matrix, Porgland cement particles (average size 10 μm) were tightly packed, corresponding to a volume fraction of cement (Portland cement volume divided by total volume) of 0.43-0.52. If an ordinary cement paste - which does not contain very fine particles - were arranged in the same way in the same way, it would correspond to a weight ratio of water to cement of 0.42 to 0.30. This is normally considered tightly packed. In the DSP material, it was still possible to incorporate up to 50% by volume of very fine solid particles into the interstices of the cement particles. The incorporated solid consisted of relatively tightly packed, very fine spherical particles with an average diameter of 0.1 μm 2 and a specific surface area of about 250,000 cm / g. The total volume fraction of solids in the matrix, comprising cement as well as silica dust, was 0.64-0.70. The weight ratio of water to solid was 0.188-0.133.

The amount of silica dust that ensures the tight packing of the silica dust particles depends on the grain size distribution of the silica dust and to a large extent the space between the tightly packed particles B. Thus, well-distributed Portland cement, which still contains 30% fine spherical fly ash particles, leaves much less space in the silica dust than the corresponding tightly packed cement, in which the granules are of the same size. In systems where particles B are mostly Portland cement, compact packing of silica dust is likely to correspond to volumes of silica dust in the range of 15-50% by volume based on particles A + particles B. Similar considerations apply to systems containing other types of particles A and B.

The principles of tight packaging are discussed in detail below in the section "Principles of tight packaging".

In the present specification and claims, the terms "very fine silica particles" and "silica dust"

SiO-containing particles having a specific surface area of ≤ 2 2 of about 50,000 to 2,000,000 cm / g, in particular about 250,000 cm / g.

Such a product is produced as a by-product in the manufacture of metallic silicon in an electric furnace and contains particles having a grain size of about 50 Å to about 0.5 microns, typically in the range of about 200 Å to about 0.5 microns.

Tight packaging of very fine powders according to the DSP principle was achieved with concrete (Example 1), mortar (Examples 3 and 9 in International Patent Application No. PCT / DK79 / 00047), and thin extruded sheets with fiberglass reinforcement (Example 2 in International Patent Application No. PCT / DK79 / 00047). In this case, the binder was made of Portland cement (specific surface area 2 about 2400-4400 cm / g) and very fine spherical silica dust (specific surface area 250,000 cm / g) arranged in a very tight package (water / powder weight ratio respectively 0 , 18 and 0.13) in such a way that an exceptionally large amount of concrete power softener (1-4% by weight, especially 2-3% by weight of power softener based on the total amount of cement and silica dust) was used as dispersant.

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The concrete was made of a highly flowable mass and has good strength (water-cured, wet, cylindrical specimens with a diameter of 10 cm and a height of 20 cm had a compressive strength of 124.6 MPa after 28 days and 146.2 MPa after 169 days). This strength is 20% higher than the highest corresponding strength values for concrete prepared and cast in the normal way, even when using power softener additives (compare Example 1 in International Application PCT / DK79 / 00047). The easily flowable mortar, which had been cured in water for 4 days at 60 ° C, had a compressive strength of 179 MPa as measured by wet specimens with a diameter of 10 cm and a height of 20 cm (compare Example 9 in International Application No. PCT / DK79 / 00047).

Pieces or particles A and B in DSP materials International Application No. PCT / DK79 / 00047 generally classifies particles A and B of DSP materials as solid particles, typically having a particle size of 50 A -0.5 μm, respectively 0.5 μm - 100 μm.

The aforementioned international patent application mainly describes compact particles, typically relatively hard materials such as Portland cement, lime, fly ash and colloidal silica. However, weak materials which are easily deformed at pressures of less than 5 kg / cm 2 are also mentioned as particles B.

According to the present invention, particles A and B can be of any shape, and a typical useful shape is an elongate rod-like body, typically in the mini-mid dimension of 50 Å to 0.5 μm for particles A and 0.5 μm to 100 μm for particles B. The length of the particles can be arbitrary and larger than the transverse dimensions, and such particles are typically chopped fibers or chips with a length / diameter ratio in the range of 10 72307 1000 / 1-5 / 1, or continuous yarn-shaped fibers.

In this specification, the term "body" means any body, such as particulate, elongated, plate-like or fibrous or continuous fiber, and the term "particles" generally means compact particles, but may also include angular particles and somewhat flattened particles. and elongated forms that are within the normal definition range of the term "particles". In addition, the term "particles" in the general description of the DSP systems of the present invention may be a common term for the term "body" when this meaning is self-evident.

The compact packaging mentioned in the explanatory note "Principles of compact packaging" relates to the geometry of the particles and the type of packaging process. Thus, a volume concentration of 10% of elongate bodies B often has to be considered too high and forms a tight package when the mixing or casting technique used to provide DSP materials containing such bodies is a simple mixing or casting technique, while the corresponding volume concentration then , when the fibers B are arranged parallel like filaments, can be up to 40-70%.

As mentioned above, the bodies can also be plate-shaped, typically having a thickness of 50 μm to 0.5 μm for particles A and 0.5 μm to 100 μm for particles B.

According to the present invention, the bodies or particles A and B can be of any chemical composition.

11 72307 1 1

One particularly interesting type of body or particle B consists of highly strong elongate particles or fibers and chips, for example metal fibers or chips, carbon fibers, rock fibers, glass fibers, N 2 O 2 chips, silicon carbide chips, graphite chips, Kevlar chips wollastonite and asbestos.

Pieces or particles A of DSP materials can serve a number of purposes: 1. They can act as building blocks that are glued together to make the material strong and rigid.

For this purpose, the material of which the particles are composed must have a chemical affinity for the "glue" formed. (This is accomplished by selecting particles A with a suitable chemical structure and / or a suitable surface treatment of the particles.) 2. The pieces A can also function to impart toughness to the DSP materials to avoid microcracking.

For this purpose, the bodies A are preferably fibers, for example 0.5 μm to 50 Å in diameter and 12,7307 100 μm to 500 Å in length, preferably 10 μm to 500 Å in length, preferably together with compact particles A, in particular such that that the concentration of compact particles A is high. Examples of suitable elongate parts or fibers A for this purpose are very fine fibers, chips and needle-shaped crystals.

3. The bodies A may also have the function of actively contributing to the formation of an "adhesive", for example when the particles A are particles which provide a solid structure when partially dissolved in interparticulate water, and a chemical reaction in the aqueous phase where the reaction product precipitates, or when the particles or fibers A are a metal that is subjected to melt-solidification or sintering in a separate step after the initial formation of the DSP matrix.

4. Pieces A can act as an accelerator or catalyst for the desired chemical processes that take place in the DSP system. Thus, particles A may be formed from ultrafine cement to accelerate the curing of cement-based DSP systems, typically cement / silica dust / concrete power softener DSP systems.

5. Particles A can act as inhibitors: 1) against corrosion, 2) against alkaline reactions, for example when particles A are SiO 2, 3) to protect glass fibers, particles A can be impermeable to ultraviolet radiation (and can preferably act as oxygen scavengers), 4 ) as toxins against biodegradation, in particular microbiological degradation; 5) as active ingredients to reduce the soluble chromate content (such as thiosulphate or ferrous sulphate) in cement; as scavengers that absorb radioactive ions from the radioactive material contained in the DSP matrix material, 7) hydrogen as rich and / or heavy elements for protection against radioactive radiation (such as lead particles).

5. The purpose of the particles A may be to impart optical properties such as reflection, transparency and fluorescence properties.

For this purpose, the particles A can be pigments whose size is adapted to the desired optical properties, in which case a size of less than 0.5 [mu] m is very effective.

6. Pieces A can be used to impart desired electrical properties (e.g., ion conduction property).

7. Pieces A can be used as electrically conductive elements.

8. Pieces A can be added as components with special dielectric properties.

9. The bodies A may be magnetic particles.

10. Pieces A may be used to impart specific chemical and thermal properties: (a) where chemical or thermal resistance is desired, or (b) where chemical or thermal resistance must be as low as possible (for example, to provide a microstructure by placing a DSP matrix containing chemically or thermally easily separable bodies A, prone to corrosion or combustion to remove the bodies A, resulting, for example, in a dense strong DPS matrix with very fine pores or holes throughout the structure).

14 72307 11. The pieces A may be of hard material to provide wear resistance of the DSP material.

Principles of tight packaging

Tight packing of particles and particles is essential in DSP systems, for example, Portland cement-based DSP materials have the essential feature of tight packing of cement particles, combined with the placement of very fine particles in the interstices of the cement particles.

In connection with the production of DSP concrete or mortar with a stable volume, it is also desirable to pack the sand and aggregate as tightly as possible, whereby the spaces between the aggregates are filled as tightly as possible with a dense DSP paste.

This package cannot be unambiguously defined, but it depends on the shape of the bodies or particles in question, their size distribution and the method of compaction.

Meaning of particle shape

The tightness of the package depends on the shape of the particles, so that the more angular, elongated and uneven the particles, the lower the seal.

In the case of DSP paste based on Portland cement, the large particles (cement) typically have a cubic shape, with a medium packaging capacity. (The shape of the cement particles depends on the manufacturing method (grinding). As far as packaging is concerned, spherical cement is ideal. Cement of this shape can be produced by generating cores and growing in the liquid phase.) On the other hand, a very fine powder contains round particles formed by condensation. . The spherical shape results in ideal packaging properties.

Tightly packed elongate particles, such as fibers, are typically arranged in a much more open structure than compact particles (compare Figure 4), unless special measures are taken (compare Figure 5).

Significance of particle size distribution

The importance of particle size distribution can be illustrated by examining binary mixtures (large and small particles) compared to multicomponent mixtures.

The compact packaging of particles, depending on the geometry of the particles (regardless of surface forces), has been discussed around the world in the literature on particle technology, for example in Particulate Technology, Clyde Orr Jr., 1966, The MacMillan Company, New York, and Principles of Particulate Mechanics, Brown and Richards, 1970 Pergamon Press. It is typical that the packaging of particle systems, where the surface forces are insignificant, is independent of the absolute particle size and depends only on the shape of the particles, the relative size distribution and the mechanical way in which the particles are placed. This means that uniform packaging of equally large spherical particles results in the same volume fraction of solid (e.g., 0.52 per cubic and 0.74 for hexagonal packaging), regardless of the absolute size of the spheres. The tightness of the package is strongly influenced by the relative particle size distribution, i.e. the relationship between different particle sizes. Thus, Brown and Richards (supra) describe classical experiments performed on binary packages of spherical particles of various sizes, in which the volume fraction of solids increases from about 0.63 for individual particle size fractions with a mixture of large and small particles of about 0.70, with an aspect ratio of 3.4 / 1, and up to 0.84 by mixing large and small particles in a ratio of 16/1. The sealing of the package is also heavily dependent on the mechanical compression method. Simple compression does not normally result in a particularly tight packaging of particle systems in which the particles retain their geometric identity (i.e., do not break or substantially alter their shape). Normally, a tighter package is achieved by shear deformation, repeated shear deformation, or balanced vibration, always applying a small perpendicular pressure to ensure that the repeated deformation ultimately results in an increasingly compact structure. For this reason, it is not possible to express the concept of compact packaging with a single feature. In this specification, the term "tight package" is to be understood as meaning a tight package which is obtained in systems without adhesive surfaces and with effects of the type mentioned above, such as shear deformation and plane-weighted vibration.

The tightest compression of all is achieved by a high ratio of large to small particles, which is typically more than 20.

At small diameter ratios, the maximum possible packing density decreases due to the wall and boundary effect, the importance of which increases as the ratio between fine particles and larger particles increases.

Without the wall and boundary effect, a 100% tight package in a multicomponent blend could be achieved by continuously filling the interparticle spaces with fibrous particles.

In practice, where the ratio between the largest and smallest particles is limited, for example in the range of about 10-10 for concrete or cement-based DSP with aggregates up to 10 mm and fine cement of the order of about 1 yum, and also for DSP also very fine

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17 72307 silica particles with an average particle size of about 0.1 μm, considerable wall and boundary power occurs if the number of individual particle fractions is more than 3 or 4, resulting in a package that is far from ideal.

There does not appear to be any theory that would allow the presentation of a grain size curve that would result in optimal packaging. Therefore, the solution seems to be a compromise between a package with only a few components and a small wall and boundary effect on the one hand, and a package with a large number of components on the other hand. In each individual case, optimum compression is achieved by performing physical compression tests in advance.

In any case, some general principles can generally be applied: 1. A tightly packed particle fraction, for example round compactly shaped fine particles in the range of 10-20 yuan, should be protected from thinning by ensuring a significant difference in particle sizes (both large and small).

2. For high-strength cement-based materials, tight sealing of cement particles that provide strength should be ensured by differences in particle size (both large and small), for example by using relatively coarse sand on the one hand and very fine particles significantly smaller than the smallest cement fraction.

3. When other particles or fibers with a size corresponding to cement, for example glass fibers with a diameter of 10-20 μm, are used in a cement-based DSP, it is possible to compensate for the relatively strong thinning of the cement fraction on the surface of these particles or fibers. , by adding a correspondingly larger proportion of very fine particles A, respectively.

The tight packing of bodies or particles with which surface forces have been eliminated is strongly dependent on the kinematics of the arrangement of the bodies. For example, the fibers can be arranged in the compact package referred to in this application by 1) a simple mixing and casting process (compare Figure 4), 2) precipitation and 3) twisting the filaments as shown in Figure 5. The density, i.e. the fiber concentration, increases strongly from case 1) through case 2) 3) reen. Typical fiber concentration values obtained by these methods are 5, 20 and 60% by volume.

Thus, it is understood that a tight pack is a combination of the shape of the particles or bodies and the manner in which the particles or bodies are arranged, i.e., the kinematics under which the concentration of particles or bodies is only negligibly affected by surface forces, such as DSP systems with efficient dispersant. .

Overcoming surface forces

An essential part of providing DSP systems is overcoming the surface forces between small particles and bodies to provide an important tight package.

In cement-based DSP, the question of providing a tight particle package is thus not essentially a question of overcoming the surface forces between the cement particles in the aqueous solution and the very fine particles.

Compact particles with a circular shape, held together by surface forces, have the ability to separate or intertwine two particles in point contact.

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19 72307 transfer forces proportional to particle size (d) and surface tension (γ) F cc yd

The surface tension γ is defined as 1) the surface tension between the liquid misk and the surrounding fluid (usually air) when the meniscus causes cohesion, or 2) the work required to create one new surface unit by moving the parallel surfaces away from the contact surface infinitely far.

Assuming that the separation and slip resistance are dominant with respect to the rotational resistance, the yield stress of the powder (proportional to the force acting on the particle divided by the particle area) can be written as p oc yd ^ or, in dimensionless form ^ = constant Ύ where constant is a function of the particle system geometry (relative particle size, shape and arrangement).

This qualitative model has shown an important part in the selection of a method for the production of dense, strong, cementitious materials, such as DSP, in which the function p £ Ύ has been used to describe the particle package.

Quantity

Pd γ is a measure of the amount where external stresses (p)

V

can overcome internal cohesion (· =).

d

Very fine particles under the influence of surface forces are typically packaged into a very open structure if the packaging takes place at a reasonable external pressure. This is the case if the particle system is packed at a very low, dimensionless compression pressure pd Y 'which results in a correspondingly low particle concentration.

Tighter packaging can be achieved by 1) greater compression, 2) reducing surface forces, for example with surfactants, or 3) selecting larger particles.

At very high values, the effect of surface forces is practically overcome, for example in a stack of stones. In principle, the packaging of particles is a matter of particle geometry, particle friction and the way in which the compression is carried out, for example by vibration.

The production of very strong and dense concrete requires the arrangement of a binder consisting of very fine particles in a tight package. However, under normal conditions, the combination of small particles, surface forces, and reasonable compressive force does not allow such a compact structure to be obtained.

According to the DSP principle, the locking effect of surface forces in cement-based materials is substantially eliminated by dispersants, allowing an ideal geometric arrangement so that small, round particles are interposed between the larger particles to ensure a very tight structure despite the fact that the particles are packed between small particles. / 100 of the size of ordinary cement particles (silica dust with an average diameter of 0.1 μm).

Il 21 72307 Thus, according to the DSP system, effective dispersants are used to convert materials based on very fine particles to a state where packaging tightness is a purely geometric and kinematic problem, as is known from the packaging theory of large particles.

According to a particular aspect of the present invention, it is also possible to perform compression of DSP materials with a higher stress field. By using compression in a high stress field, it is possible to successfully provide DSP systems based on the smallest particle size in the range indicated for particles A, i.e. 50-200 A, where at surface forces (γ) the model pd - = constant

Y

is of growing importance. By increasing the compressive stress p accordingly, the level pd Ύ which is characteristic of the surface forces being overcome can be maintained.

In other methods for arranging fine bodies or particles, such as precipitation, similar principles can be used, only the mathematical models are different. Thus, achieving a tight arrangement by precipitating small fibers depends on whether the gravity acting on the fibers is large enough to overcome the surface forces that tend to fix and lock the precipitated fibers (such fixation is typically one that tends to fix the fiber to a completely undesired position not parallel to with the fibers) so that the descending fiber is in the desired position substantially parallel to the already descending fibers.

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Effect of dispersant in Portland cement / very fine particles system_

The dispersion of fine particles using surfactants has been widely described in the literature on colloids and surface effects.

The purpose of using a surfactant is to provide such repulsive forces relative to adjacent particles that these forces can overcome the mutual attraction of the London / van der Waal forces, as well as possibly other attractions. The aim of this means is to eliminate the adhesion between the particles, so as to ensure the sliding of the particles with each other, which is absolutely essential for obtaining a tight package with low compression.

According to classical theory, two separate pushing mechanisms are normally considered: electrical repulsion caused by the formation of an electrical double diffusion layer in the material surrounding the particles (compare DLVO theory), and steric hindrance, which prevents particles from adhering to each other (i.e. their flocculation) by adsorbing them. .

Such adsorbed layers may be medium molecules, or they may be surfactant molecules. The physical interaction of the adsorbed molecules as the particles approach each other acts to prevent flocculation. It is believed that the steric barrier effect is a determining factor when the cement is dissolved in water by the action of typical concrete softeners, but that electrical repulsion also participates in the mechanism in addition to the former.

Many years of experience show that the pure electrical repulsion effect is insufficient to prevent Flocculation of Portland cement in water (probably due to the high concentration of divalent and trivalent counterions Ca ++ and Al +++) which, according to the Hardy-Schultz rule, reduces diffusions 23 7230 double layer, and possibly also due to the formation of direct chemical bonds (or bridges). It seems likely that the effective dispersion of normal Portland cement in water is heavily dependent on dispersants that provide an effective steric barrier.

Achieving a good dispersion in very fine silica, i.e. with an average grain size of 0.1 μm, is in principle much simpler than obtaining a corresponding dispersion with much coarser Portland cement (typically having an average particle size of 10 μm).

Thus, efficient dispersion of colloidal silica in water (without salt content) is achieved by pH adjustment (typically pH above 7 or 8), as described in Surface and Colloid Science, Egon Matijeviec, Ralph K. Iler, 1973, John Wiley & Sons). Practical experience with the fine silica dust used in the examples of the application (specific surface area about 250,000 cm / g) shows the same general behavior.

Thus, a 1/1 mixture of silica dust and tap water (by weight) and a 2/1 mixture of silica and 3% aqueous sodium tripolyphosphate both result in solutions of reasonable viscosity that can be easily mixed with low power mixers or by hand. However, attempts to combine such silica / water systems with Portland cement will result in increased flocculation.

Thus, the addition of a small amount of a flowable Portland cement / water solution (typically a water / cement ratio of 1) to a large amount of a silica / water solution of the above type and concentration (i.e., typically 1 part cement solution to 10 parts silica / water solution) results in appreciable solidification. , which makes any further mixing impossible.

24 72307 This indicates that the cement dissolved in water eliminates the dispersion of very fine silica particles. The exact mechanism of bond formation between silica particles is not known, but the explanation is likely to be that bilayer repulsion is reduced and that various direct bonds or bridges are formed.

Using power softeners in concrete, such as the sodium salt of formaldehyde condensate via strongly condensed naphthalene sulfuric acid, which typically contains more than 70% of molecules with 7 naphthalene cores or more, it is easy to obtain a very good dispersion in a combined finely divided silica / Portland cement system. which allows the binder to be tightly packed in a low stress field.

Thus, the effect of power softeners in very fine particle / cement / water DSP systems is not due to their ability to disperse very fine particles in water (in fact, other surfactants are better for this purpose), but to their ability to provide good dispersion of silica here. in a specific Portland cement / water environment.

Structure and Properties of Composite Material The present invention provides several novel methods and principles for providing DSP materials, which methods are described in the following sections of the specification. This section is particularly concerned with the provision of high-strength cement-based DSP materials.

The strength of ordinary concrete depends primarily on the quality of the cement binder, which binds the sand and stones together, and only to a lesser extent on the quality of the sand and stone as long as the normal materials are involved.

72307 The reason for this fact is that the binder is the weakest link in ordinary concrete and that the cracks occur mainly in the binder and do not pass through the sand and stone particles.

In concrete structure design books, this has been explained by assuming, as a first approximation, that strength is only a function of binder composition (expressed as cement concentration in a cement-water suspension as a water / cement ratio), without including sand and stone quantity or quality in the models.

In concrete where the strength of sand and stone is no longer high relative to the strength of the binder, both the strength of the binder and the strength of the sand and stone are important in view of the strength of the composite material.

This is a known fact with aerated concrete, where the aggregate consists of a light, porous, relatively weak material. In this case, the internal strength of the aggregate is as important as the strength of the binder when the strength of the concrete is mathematically expressed: n 1-n σ = σ x σ am where σ is the compressive strength of the concrete, σ is the compressive strength of the stone, am is the compressive strength of the binder, n is the concentration and 1-n is the volume concentration of the binder. In such materials, cracking proceeds to a considerable extent through weak rock particles.

The development of a new high-strength cement-based DSP binder, described in International Application No. PCT / DK79 / 00047, has provided concrete and mortar with hitherto unknown strengths. Thus, International Patent Application No. PCT / DK79 / 00047 discloses water-cured wet cylinder test pieces with a diameter of 10 cm and a height of 20 cm and a compressive strength of 146.2 MPa for concrete after 169 days of storage at 26 72307 at 20 ° C and 179 MPa for a mortar cured at about 60 ° C for 4 days. Both concrete and mortar were made from easily flowable casting compounds with weak mechanical vibration. Conventional quartz sand and granite for concrete were used. The strengths were compared to the highest strengths reported in the relevant technical literature: 120.6 MPa measured for test cylinders with the same dimensions as above and consisting of concrete with a water / cement ratio of 0.25, a cement content of 512 kg / m 2 and "Mighty" 150 content (the concrete power softener described in more detail below) in an amount of 2.75% as a 0.42% solution, calculated on the amount of cement, in which the samples had been stored for one year before the compressive strength test. (Kenichi Hattori, "Superplasticizers in Concrete, Vol. I, Proceedings of an International Symposium held in Ottawa, Canada, May 29-31, 1978, edited by VM Malhhotra, EE Berry and TA Wheat, Sponsored by Canada Center for Mineral and Energy Technology, Department of Energy, Mines and Resources, Ottawa, Canada and American Concrete Institute, Detroit, USA.)

Examination of fracture surfaces in connection with strength measurements described in International Patent Application No. PCT / DK79 / 00047 showed that the sand and aggregate used were not strong enough compared to the binder, as would be the case for normal concrete, as fracture progressed significantly between sand and stone particles. through.

This showed the possibility of producing even stronger concrete by combining the use of DSP binder with the use of much stronger sand as well as aggregate. This is a principle that has no significant significance in the context of normal concrete, as described above.

27 72307 Combining a DSP binder with particularly strong sand and aggregate is one of the most important aspects of the present invention.

In accordance with this aspect, concrete and mortar were prepared using DSP binder as well as refractory bauxite and silicon carbide as sand and aggregate, both of which are much stronger than sand and aggregate of ordinary concrete, compare Examples 1 and 4.

Concrete and mortar were made of easily flowable masses and had excellent high strength (compressive strength of cylindrical concrete bodies with a diameter of 10 cm and a height of 20 cm and hardened at 60 ° C for 4 days was 217 MPa).

This is more than 50% higher than the strength of very hard concrete made of ordinary sand and stone, bonded together with a new strong cementitious material (146.2 MPa, cf. International Patent Application No. PCT / DK79 / 00047) and more than 20% higher than the highest strengths obtained, to the applicant's knowledge, from concrete produced by conventional soft-mass casting and curing using conventional special-softened binders (120.6 MPa, cf. Hattori as mentioned above).

The new high-quality material 011 according to the invention also has an extremely high stiffness (dynamic modulus of elasticity 109,000 MPa), which is about 60% higher than high-quality concrete using DSP binder and quartz sand and granite, cf. International Patent Application No. PCT / DK79 Example 1.

The mortar made of refractory bauxite sand was even stronger and stiffer than concrete (compressive strength of cylindrical bodies with a diameter of 10 cm and a height of 20 cm, cured at 80 ° C for 4 days, was 248 MPa 28 72307 and the dynamic modulus of elasticity was as high as 119 000 MPa, compare Example 3). Compressive strength is 38% higher than the strongest mortar made with DSP binder and quartz sand (179 MPa, compare Example 9 of International Patent Application No. PCT / DK79 / 00047), and more than twice as high as the above-mentioned strong concrete according to Hattor (120 MPa). Even stronger cement-based DSP materials according to the present invention are provided with strong sand and aggregates, cf. Example 4, where the strength was 268.3 MPa.

Thus, the DSP concrete material of the present invention has a hitherto unattainable quality achieved by using high-strength sand and aggregate in combination with a high-strength DSP binder, whereby 1) the strength of sand and aggregate is better utilized compared to ordinary concrete, and 2) The strength of the DSP binder is much better utilized than in concrete with ordinary sand and aggregate.

Together with the benefits of easy production associated with the DSP binder, the particularly strong sand and aggregate opens up the possibility of producing a wide range of new and improved products.

Another very interesting view for very strong, cement-based DSP materials is the ratio of strength σ to density p, which is a key parameter in the construction of large structures such as towers, bridges, etc., where the maximum possible size is proportional to this ratio. The strength / tightness ratio of cement-based DSP materials, and in particular DSP materials containing sand and aggregate, is considerably higher than that of ordinary concrete or high-quality concrete and even higher than the strength-to-tightness ratio of structural steel.

29 72307

The invention relates to a shaped body comprising high-strength cement-based DSP materials, as defined in the appended claim 1.

According to the above-mentioned aspect of the invention, sand and aggregate are used which are stronger than the sand and aggregate used in ordinary concrete. Concrete sand and stone typically consist of ordinary stone such as granite, gneiss, sandstone, flint, and limestone, including minerals such as quartz, feldspar, mica, calcium carbonate, silica, and the like.

Various comparative tests can be used to determine that certain sand and stone materials are stronger than ordinary concrete sand and stone, for example 1) hardness measurement 2) determination of the breaking strength of individual particles 3) hardness measurement of minerals consisting of sand and stone materials 4) powder compression resistance wear tests 6) grinding tests 7) measurement of the strength of the composite material containing particles.

It is difficult to define unambiguous relationships between such strength and hardness results for sand and stone, and the ability of sand and stone to increase the strength of concrete or mortar.

In general, it must be assumed that sand and aggregate with higher hardness, abrasion resistance, strength in composite structure, etc. will lead to higher strength in concrete provided 1) identical particle geometry (particle shape, particle size, number and degree of packaging) and 2) that the concrete systems are s , in which, to a certain degree, fracture occurs through sand and rock particles. (If the latter condition is not met, this is because, as mentioned at the beginning of the description, sand and aggregate are in any case clearly stronger than the matrix and that increasing the strength of sand and aggregate does not affect fracture in any way, breaking through the matrix in any case avoiding sand. and stone particles.)

Examples 1, 2, 3 and 4 use sand and stone materials with significantly higher strength and hardness than ordinary concrete: Refractory bauxite containing 85% (corundum) as well as silicon carbide was used. Both materials have significantly higher hardness than minerals found in ordinary sand and rock. Thus, both corundum and silicon carbide are reported to have a hardness of 9 on the Mohs hardness scale, and Knoop’s notch hardness is reported to be 1635-1680 for alumina (corundum) and 2130-2140 for silicon carbide, while quartz, one of the hardest minerals in ordinary concrete sand and stone, has Mohs hardness 7 and Knoop notch hardness 710-790 (George S. Brady and Henry R. Clauser, Materials Handbook, 11th edition, McGraw - Hill Book Company).

The high strength of these materials compared to ordinary concrete sand and stone has been demonstrated by powder compression tests (Example 2) as well as tests on mortar and concrete containing silica cement binder, where these materials were used as sand and stone (Examples 1, 3 and 4).

Il 31 72307

Several materials other than the two mentioned above can, of course, be used as strong sand and aggregate. Typically, materials with a Mohs hardness greater than 7 can be used, for example, topaz, legalonite, diamond, corundum, phenacite, spinel, beryl, chrysoberyl, tourmaline, granite, andalusite, staurolite, zirconium, boron carbide, borocarbide.

The hardness criterion can also, of course, also be expressed as Knoop notch hardness, in which case minerals with values above the value of quartz (710-790) must be considered as strong materials compared to ordinary concrete sand and rock-forming minerals. To determine the strength of sand and stone, the technique described in Examples 1, 3 and 4 can be used, comprising incorporating the sand and stone in question into a specific cement / silica matrix prepared and tested in a specified manner:

Concrete (largest particle size exceeds 4 mm):

Concrete made of ordinary concrete sand and stone (granite stone and quartz sand) and silica / cement matrix, which was substantially identical to that used in Example 1, had a compressive strength of about 120-160 MPa (cf. International Patent Application No. PCT / DK79 / 00047). Therefore, it seems reasonable to characterize stone and sand, which increase the compressive strength of concrete by 170 MPa, as strong as compared to ordinary concrete sand and stone. However, with refractory bauxite sand and stone, a strength of 217.5 MPa compared to Example 1 of the present application was achieved, therefore values above 200 MPa can be considered a realistic and desirable goal for the desired material.

Mortar (particle size less than 4 mm): 32 72307

A similar experience has been gained with cement / silica mortar, where materials with substantially identical cement / silica matrix resulted in a compressive strength of 160-179 MPa for quartz sand mortar (compare Example 9 of International Patent Application No. PCT / DK79 / 00047) and 248 and 268 MPa of refractory b, respectively. mortar (Examples 3 and 4 of the present application, respectively). It seems reasonable to characterize sand that increases the strength of the mortar by more than 200 MPa, strong compared to the strength of normal sand, and it also seems reasonable to consider strengths of more than 220 MPa as both a desirable and achievable goal for recommended materials.

For the evaluation of aggregates with a particle size exceeding 4 mm, the concrete technique according to Example 1 is used. For grading sand with a particle size of less than '4 mm, a mortar technique is used, compare Example 9 of International Patent Application No. PCT / DK79 / 00047 and Examples 3 and 4 of the present patent application (combination as for bauxite mortar), where different volumes of sand must be used in different mixtures. and aggregate, and not the same weight-amount of sand and stone. The preparation, curing and testing are carried out as in the examples mentioned.

The above test methods, as well as the particular way in which certain tests are performed, form the basis for the definition of useful and recommended particles C referred to in the requirements.

The added material D, at least one of the dimensions of which is an order of magnitude larger than the particles A, can in principle be solid bodies (as will be described in more detail later), a gas (as in aerated concrete) or a liquid. The material can be compact shaped pieces (such as sand, rocks, gas bubbles, or liquid bubbles), plate-shaped pieces (such as mica), or elongated pieces (such as fibers, reinforcing bars, or wires). Due to the ability of 33 72307 to mold the articles in question in a "soft" manner in a low stress field, such articles may, in contrast to all known compaction processes where it is possible to achieve tight compression with ultrafine particle systems, retain essentially their geometric identity during molding. In this context, the preservation of the geometric identity shows that the pieces in question are not subjected to crushing or strong transformation. A typical example is a hollow body or fiber which would be severely broken or deformed in powder compaction or other high voltage treatments, but which in a much lower stress field, where the articles of the invention are also molded, can be made without such deterioration.

Examples of added material D, which is preferably combined with the DSP matrix, include sand, stone, polystyrene pieces including polystyrene beads, expanded clay, hollow glass pieces including hollow glass spheres, expanded clay stone, perlite, natural lightweight concrete filler, gas light concrete filler, gas metal fibers such as steel fibers, plastic fibers, glass fibers, Kewlar fibers, asbestos fibers, cellulose fibers, mineral fibers, high temperature resistant fibers and "chips", including inorganic, non-metallic chips such as graphite chips and Al 2 OA chips and metal chips and metal chips; chips, heavy components such as barite or tin or tin-containing minerals, and hydrogen-containing components such as hollow, water-filled particles. When the articles of the invention contain additional material D, it may be interesting to provide tight packages of additional material due to optical strength and stiffness or other considerations. The easily transformable (easily flowable) DSP matrix made possible by the present invention allows for a much denser order of additional material than that provided by the prior art.

34 72307

The joining of the fibers in particular is very interesting due to the unique ability of the DSP matrix to attach them. In this context, it should be mentioned that the much denser structure of the moldings containing the DSP matrix practically results in the isolation of fibers that would otherwise be chemically attacked by the components of the matrix or the environment. The fibers used in the articles of the invention may take any form, such as chopped single fibers or continuous fibers or yarns or ropes, or pre-spun or strong fibers, or fibrous nets or fabrics. The specific type and shape of the fiber depends on its specific use, with the general principle that the larger the dimensions of the shaped body, the longer and coarser the fibers are preferred.

Improved adhesion of fine fibers allows for the production of significantly improved fiber composite materials based on mixing a greater amount of chopped fibers into the material than in conventional matrix-based materials. In order to ensure good organization of the fiber in a known matrix, it is necessary that the chopped fibers have a certain (large) length in relation to the diameter, the so-called the aspect ratio. However, in normal matrices, it is difficult to mix and arrange the fibers at high aspect ratios - i.e., the lower the aspect ratio, the easier it is to add fibers and arrange them appropriately in the casting rice, and the larger the volume of fibers can be added. For example, chopped polypropylene fibers having a cross-sectional dimension of about 30 microns are usually 12 to 25 mm long (aspect ratio greater than 500) when used as reinforcements in conventional cement matrices. Much better use of fibers of the same type has been achieved in the matrix according to the invention, as described in Example 2 of International Patent Application PCT / DK79 / 00047. Example 2 of International Patent Application PCT / DK79 / 00047 gives a very advantageous attachment of the bond 35 7230 7 and as a result advantageous strength properties even though the fiber length was only 6 mm. In the DSP matrix, it seems possible to reduce the length of the chopped fibers and therefore the aspect ratio by a factor of 10 or more (compared to the ideal and actual chopped fiber aspect ratios used in the normal matrix) and accordingly take advantage of this reduced aspect ratio by adding larger amounts of fibers to the composite and / or order in the casting material.

The above-mentioned polypropylene fibers used in Example 2 of International Patent Application PCT / DK79 / 00047 can be characterized as polypropylene fibers having a tensile strength of at least 4000 kp / cni, a modulus of elasticity of at least 7-10 * kg / cin and an elongation at break of up to 8%. Such fibers can be made by stretching the polypropylene film in a ratio of at least 1/15, the film then becoming 10-60 yU thick, and turning the stretched material into 2-35 dtex fiber filaments by means of a rotating needle or cutter. This technique is disclosed in German Patent Application No. P 28 19 794.6 and U.S. Patent No. 4,261,754.

Among the most important articles containing a DSP matrix are articles in which the particles B contain at least 50% by weight of Portland cement particles, and in particular articles in which the particles B consist essentially of Portland cement. This very important group of shaped bodies (whose strength is described in the example) typically contains silica dust particles 5-50% by volume, preferably 10-30% by volume, of the total volume of particles A and B and sand and stones as additional material to form very high quality mortar or concrete for mechanical strength, frost durability, etc., and / or fibers, especially metal fibers, including steel fibers, mineral fibers, glass fibers, asbestos fibers, high temperature resistant fibers, carbon fibers, and organic fibers, including plastic fibers. With respect to fibers exposed to chemical stress, such as glass fibers subjected to severe weathering conditions, an important advantage of the present invention is that such fibers become much better protected against environmental influences both during curing and in the final cured material due to partial dissolution of silica dust by alkaline neutralization. , and due to the microtective curtain of ultrafine particles and coherent structure around the fibers, which very substantially promotes static conditions in the glass fiber environment, especially avoiding mixing of the alkaline material against the fiber in the final cured material.

When the shaped bodies according to the invention are large, they are preferably made of steel, such as steel bars, rods, nets or fibers. In prestressed constructions containing a DSP matrix, reinforcements are very relevant. Because the articles can be molded under very mild conditions, the reinforcements retain their geometric identity during the molding process. In the prior art, it was hardly possible to produce combinations with, in addition to the matrix structure described above, a reinforcing steel that has retained its geometric identity during the molding process.

As the strength of the binding matrix and the adhesion of the fibers and rods to the matrix increase sharply, it is possible to produce new types of reinforced and fiber-reinforced cement-based articles and materials: 1) High tensile brittle materials obtained fibers and chips, for example glass fibers, carbon fibers, asbestos, Al 2 O 2 chips) in the medium in a high volume concentration to form a bonding matrix.

2) Semi-brittle materials with high tensile strength and relatively high stress resistance, obtained by combining high quality relatively fine fibers with high tensile strength and relatively low modulus of elasticity in a medium with a high volume concentration into a bonding matrix (e.g. strong polypropylene fibers) and Kevlar fibers.

3) High quality prestressed reinforced articles, the quality of which is mainly obtained by combining much larger volumes of high quality steel bars or wires than are commonly used (the volume of reinforcement that can be utilized being directly proportional to the compressive strength of the matrix) in the new types of matrices of this invention. In ordinary prestressed concrete, the volume of prestressed steel is 1-2% of the concrete.

The volume of steel is limited by the compressive strength of the concrete. Increasing the compressive strength by a factor of 4 could be fully utilized in a prestressed component by ensuring fourfold bending strength or by halving the height of the component.

Such components would require unrealistically high volumes of prestressed steel (4-8%). It would also be possible to apply the improved matrix material to prestressed articles with a much smaller cross-sectional area than in traditional prestressed concretes, while correspondingly using finer prestressed reinforcements (thin wires). Despite the large specific surface area, the new dense matrix material effectively protects the wires from all environmental influences.

38 7230 7 4) Non-prestressed, reinforced concrete articles, where a better quality matrix material is primarily utilized by joining steel bars or wires with much higher tensile strength than in ordinary steel-reinforced concrete. Using larger amounts of conventional preparations to obtain a better quality matrix would in many cases require the use of unrealistically large amounts of reinforcements. The surface of the high-quality reinforcing bars used in ordinary concrete is shaped to ensure that they adhere to the concrete (molded bars # brushed steel; tent steel, etc.). The strength of such bars, 900 MPa, is not the same as that of the best cold-drawn bars and wires used, for example, in prestressed concrete, which typically has a strength of 1800-2200 MPa. On the other hand, smooth wires and rods do not ensure adequate attachment to ordinary concrete. The greatly improved adhesion provided by the DSP matrix allows the use of very strong, smooth steel wires and rods as unstressed reinforcements. When using perfectly high quality steel, due to the high stress and resulting cracks - which occur in concrete (such as ordinary reinforced concrete) - it is recommended to use the above technique in structural parts together with fine reinforcements, the type of cracking is confirmed into several finely divided thin cracks.

Said reinforcement can, of course, be combined in many ways, for example by making a thin shell of semi-brittle reinforced material into a large load-bearing component, or by using high-grade steel wires as secondary reinforcements (placed mainly perpendicular to the main reinforcement) in large prestressed components.

39 72307

When strong sand and stones (material C) are incorporated into the matrix according to the aspect of the invention described above, the resulting high quality DSP materials can be characterized as having a compressive strength of more than 150 MPa, preferably more than 180 MPa, measured on a test piece with a diameter of 10 cm and a height of 20 cm in the case of the largest compact bodies greater than 4 mm and more than 180 MPa, measured on a test piece 3 cm in diameter and 6 cm high, in the case of the largest compact bodies not exceeding 4 mm, provided that the shaped body: has at least one dimension of at least 1 m, and a cross-section of at least 0.1 m, and / or a complex shape which cannot be achieved by powder compression.

Flow structure properties; water retention By adding very fine particles to the compartments of tightly packed particles, for example silica particles with a specific surface area of 250,000 cm 2 / g, in the compartments of cement particles with a diameter of about 5 μm, a structure with improved resistance to internal mass transport is obtained, as a transport of a fluid (gas or liquid) between particles and by mass diffusion into a liquid in the pores.

The extrusion of water from impregnated particle systems depends on the compression of the particle structure - which typically depends on whether there is a transition between the particles - and on the flow of liquid in the channels between the particles.

When forming cement-silica-water suspensions, internal fluid transport in fresh material is critical. The resistance to the viscous flow of liquid between particles in systems with geometrically similar particles varies inversely with the square of the particle diameter.

This means that the fluid transport time due to the pressure gradient in two geometrically similar particle-liquid systems with a particle size ratio of 1/50 is 2500 times longer in a fine system than in a system containing 50 times larger particles.

A similar effect is achieved by filling the pore volume between the larger particles with very fine particles, since the cross-sectional dimensions of the channels between the resulting particles are crucial for the resistance to flow. The effect of particle size on water retention is further illustrated in Figures 6, 7 and 8. These conditions are well known, and it is also known to reduce internal fluid transport in cement / water systems by adding to water so-called "thickeners" in the form of very fine particles or polymers such as Metocell.

However, due to the dominant effect of the fixing surface forces, it is not normally possible to combine 1) the use of a very dense cement pack and 2) the use of very fine particles in an easily flowable aqueous suspension.

However, with extremely high dosages of a dispersant such as a power softener, this is possible. Thus, a flowable cement paste, mortar and concrete with tightly packed cement particles and containing 10-30% by volume of silica dust, based on the amount of cement + silica dust, can be prepared, the water / cement + silica dust weight ratio being 0.15 -0.20.

This provides several advantages over known methods: il 41 72307 1. Preparation of a highly flowable cement product without leakage.

In the known production of high quality concrete and mortar using relatively large amounts of power softeners, an easily flowable mass with a low water / cement ratio (e.g. 0.25) is obtained. The mass is poured into a mold where it is compressed by gravity and possibly also by mechanical vibration. In this process, however, the heavier cement, sand and stone particles tend to organize into an even tighter package, while the water escapes upwards in the so-called leakage, compare Figure 7.

In known systems with very efficient cement dispersion, which is achieved by using relatively large amounts of power softeners, a clear leak is normally observed despite the low water / cement ratio - especially when the process also involves vibration. This phenomenon can be critical, for example, when pouring concrete roads with power-hardened concrete, as leakage will result in an overflowing slurry with a higher water content and therefore may lead to a road surface of lower quality than the intended tread. Internal water separation is also critical when pouring reinforced concrete with power softeners. Separation of water can also lead to leakage below the reinforcement, which reduces the adhesion of the reinforcement as well as protects against chemical corrosion.

When very fine particles are added according to the principles of the present invention, for example 5-15% siliceous dust of the above-mentioned particle size, between tightly packed cement particles and using a high dose of power softener, a decisive leakage deceleration is achieved, theoretically 100-1000 times smaller water movement (compare Figure 8). In practice, this means that leakage is avoided given that the chemical structuring process normally begins and develops much faster.

42 7 2 3 0 7

Ts. by utilizing the above-mentioned principle of the invention, according to which a high dosing of the power softener is combined with silica dust, it becomes possible in practice to produce high-quality highly flowable concrete, mortar and cement paste without leakage. This is particularly interesting in the case of prestressed structures, where the above principles can be used to produce a high quality leak-proof easy-to-run grout that fills the prestressed reinforcement with excellent protection and extremely good mechanical bonding, compare the detailed description below.

2. Manufacture of high quality cement products with low stress field and without liquid transport to the environment.

In the manufacture of certain cement products, for example asbestos-cement tiles, the prior art uses either a slip casting technique (where excess water is squeezed out of the aqueous solution through filters, compared to a magnesium process where extrusion is effected by a vacuum system) or extrusion of high pressure wet powder to avoid avoidable internal water transport at the outlet and to avoid consequent clogging of the system due to particle interconnection).

According to one aspect of the present invention, it is possible to produce such materials in a low stress range by simple rolling methods or extrusion without releasing water into the environment when a large amount of a power softener is added to the pulp together with very fine particles.

Although it might seem possible to use similar rolling or extrusion methods with cementitious materials to which large amounts of power softeners have been added, but without the simultaneous use of very fine particles, which is characteristic of this aspect of the present invention, such materials can be made - although easily flowable with a low water / powder ratio (but not as small as with very fine, well-dispersed particles) - due to the larger size of the cement particles, a clear tendency for local water extrusion in stress areas such as rollers or extruder mouth resulting in particle clogging. This has been observed in practical experiments performed with a laboratory extruder using power-softened fine cement as well as power-softened ordinary cement + addition of a fine filler that was finer than cement but substantially coarser than the very fine silica dust mentioned above. In both cases, the material behaved like sand and could not be extruded due to clogging.

When very fine silica dust is incorporated into a power-softened cement system in accordance with the principle of the present invention, such water extrusion is slowed down by a factor of the order of 100-1000 (calculated theoretically). Cement-silica material containing a large amount of a power softener behaves visually viscously, staying together during rolling, while similar power-softened products without very fine silica dust typically behave as friction materials that tend to localize the extrusion or blockage of the water extraction.

3. Manufacture of flowable materials with good internal cohesiveness.

72307 44

Easily flowable power-softened cementitious materials containing very fine silica particles are an aspect of the DSP principle and have much better internal cohesiveness than the corresponding power-softened easily flowable cementitious materials without very fine-grained silica particles. It is assumed that this is due to the fact that the local liquid transport, which contributes to the separation, is decisively reduced in materials with very fine silica particles.

(This is shown in Figure 10, which illustrates the internal cohesiveness of a plastic mortar fluid. Exposure to running water (4 liters per minute) typically for 5-30 minutes does not result in a noticeable removal of materials from the mortar.) In this way, several advantages are achieved. For example, a substantial improvement has been achieved in the possibilities that already exist to produce underwater concrete simply by pouring fresh concrete into water.

This technique is known per se and has been specially developed in combination with power softener additives (without a very fine powder. Combined with a very fine, well-dispersed silica powder according to the principles of the present invention, however, the process is much more attractive and has correspondingly wider potential applications.

Resistance to internal fluid transport increases as the tightness of the packaging of very fine particles increases between coarse particles. Therefore, it is expected that flowable powder materials consisting of well-dispersed Portland cement (s = 4000 2 2 cm / g) and silica dust (s = 250,000 cm / g) would have much better internal cohesiveness, better resistance to internal fluid flow, and against leakage and a better workability of the batch 45 72307 when rolling and extruding 20-40% by volume of silica dust than 5-10% by volume of 11% by volume of silica dust. However, experience to date shows that even small amounts of very fine silica dust (typically 1-5%) incorporated between the tightly packed particles B, especially the tightly packed Portland cement structure, can have a decisively improving effect compared to similar materials without silica dust.

Other important aspects of the present invention are the filling of channels and cracks with a cured filling mortar.

The filling mortar usually consists of cement and water, usually containing additives to improve the properties. Subsequent filling of channels in prestressed concrete elements has two main purposes; preventing corrosion of wires and providing a bond between prestressed steel and concrete. The most important properties of the mortar pumped into the ducts are fluidity and water retention (small leakage).

Flowability is essentially a function of the water / cement ratio. As the water content decreases, a stiffer and less fluid mixture is obtained, and this phenomenon is more pronounced with a low water / cement ratio. In general, the water / cement ratio in a good mortar is between 0.35 and 0.50. There are a number of additives, such as dispersants, which improve the flowability at a certain water / cement ratio, or alternatively reduce the water / cement ratio required to achieve high flow properties, but their effect on other properties of the mortar, especially the tendency to leak, often limits their use.

Before the filler hardens, water may separate from the mixture due to the fact that the solid particles are heavier than water (a phenomenon often referred to as "leakage").

46 72307 This can e.g. causes unwanted water gaps on the underside of the prestressed steel. Leakage increases with increasing water / cement ratio as well as with increasing amount of dispersant (e.g. in a liquid cement paste with a water / cement ratio as low as 0.25, which is achieved with a high dosage of concrete power softener, a clear leak occurs despite a very low water / cement ratio). Anticoagulant additives are available that provide a thixotropic blend with virtually no leakage. However, to date, no combination of high flowability and very low water / cement ratio has been present in any of these additives. In addition, most of these additives are based on cellulose ether, which degrades strength as well as slows down curing. The filler mortar of the present invention (e.g., a cement-silica-Mighty filler with a water / cement plus silica dust ratio of 0.15 to 0.18) achieves the following: 1) A much denser and stronger filler with improved prestressing steel adhesion (probably corresponding to PC10 / DK79 / 00047 Example 10) and the corrosion protection of steel, whereby 2) this filling mortar, despite the extremely low water / powder ratio, is easily flowable and suitable for pumping into ducts to fill them practically without air. leakage, in which case additives (very fine inorganic particles such as silica dust and a power softener for concrete) have no detrimental effect on the hardening of the mortar, in contrast to 3) very high strength is achieved at an early stage.

In the case of post-stressed concrete, the aggregate to be injected into the channels does not normally contain coarser particles (sand), as this would impair the flowability of the mass. According to the present invention, the filler may as well

II

47 72307 as a conventional filler without sand content or other additives. The greatly improved adhesion of the flowable mass according to the present invention without leakage makes it possible to add sand to the filling mortar and thus to obtain an even stiffer hardened structure, while the filling mortar remains easily flowable. An experiment has been shown (Example 11 of International Patent Application No. PCT / DK79 / 00047) in which a flowable cohesive cement-silica mortar containing sand up to 4 mm was easily poured into a very narrow channel (diameter 18 mm) about 2.5 m long. , mainly by gravity, resulting in a very dense structure.

In the same way, the invention also makes it possible to produce substantially improved compressed concrete (in which a flowable mortar was filled between the pre-arranged stones). The improvement provided by the leak-proof, highly flowable mortar of the present invention can be used in both dry casting and underwater casting.

One particular method for injecting filler material is to ensure both good filling of narrow spaces (typically with paste) and filling of large-volume cavities between coarser particles (typically with concrete) in a two-step process starting with mortar and ending with concrete.

methods of Preparation

The moldings according to the invention can be produced in a low stress range starting from the composite material according to the invention as defined in the appended claim 24.

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It should be noted that although the amount of surfactant dispersant is defined in claim 3 by specifying the conditions that must be met for the amount to be sufficient to disperse the particles under a low stress field (i.e., expressed as the use of an excellent amount of surfactant dispersant), this does not mean that the composite material is necessarily used with a low stress field; it can be used at higher stresses. Articles containing tightly packed very fine particles are obtained from a composite material of the type mentioned above, in which particles A are present in a volume substantially corresponding to a tight package, to fill the cavities between the particles B when these are tightly packed.

The surfactant dispersant is present in an amount sufficient to allow tight sealing of the particles A with a low stress field of less than 5 kg / cm, preferably less than 100 g / cm, and the ideal amount of dispersant is substantially equivalent to the amount that fully satisfies particle A surface. Figure 1 of International Patent Application No. PCT / DK79 / 00047 shows very fine silica particles coated with a layer of dispersant, the so-called with the power softener "Mighty", the composition of which is described below. Provided that the power softener is absorbed as a uniform layer on the surface of the silica spheres, the thickness calculated from the applicant's own experiments was 25-41 Å, corresponding to a volume of 14-23% of the volume of the spheres. It should be noted that an excess of dispersant in addition to the amount which completely fills the surface of the very fine particles is not preferable and only tends to fill more space in the composite material.

A dispersant of any type, in particular a power softener for concrete which sufficiently disperses the system with a low stress field, is suitable for the purpose of the invention 49 7 2 3 0 7. In order to obtain very valuable results in the Portland cement-based systems, the concrete power softener described in the examples is of the type containing an alkali or alkaline earth metal salt of a highly condensed naphthalenesulphonic acid / formaldehyde condensate, especially a sodium or potassium salt with more condensate. % by weight consists of molecules containing 7 or more naphthalene cores. One commercially available type of this type is called "Mighty" and is manufactured by Kao Soap Company, Ltd., Tokyo, Japan. The Portland cement-based composite materials containing silica dust according to the invention use this type of concrete super softener in an amount as high as 1-4% by weight, in particular 2-4% by weight, based on the total weight of Portland cement and silica dust.

Other types of concrete power softeners that can be used for the purpose of the present invention include:

Lomar-D Concrete superplasticizer with the same composition as Mighty and manufactured by Diamond Shamrock Chemical Company, N. Jersey, USA.

Melment Anionic melamine resin solution.

Betokem Naphthalene and lignosulfonate-based sulfonic acid formaldehyde condensate.

Sikament Naphthalene-based sulfonic acid formaldehyde condensate.

Portland cement-based composite materials of the type described above often further comprise fine particles of suitable size and size distribution together with Portland cement particles such as fine sand, fly ash and fine lime to provide even denser binary structures from particles B according to the principles described above.

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In view of both its excellent design and handling properties, which have been described and illustrated in more detail in the examples above, and its ability to gently hold and effectively micro-lock or micro-enclose any added accessories in the pre-formed state, the composite material has unique advantageous advantages. and not disclosed for any material, and thus these new and excellent useful composite materials constitute the main objects of the present invention.

Interesting new composite materials according to the invention are materials based on Portland cement or non-Portland cement, which additionally contain pieces selected from the group consisting of polystyrene bodies, e.g. polystyrene balls, expanded clay, hollow glass pieces, e.g. hollow glass spheres, expanded clay, perlite, natural light stone, gas bubbles, fibers, e.g. metal fibers such as steel fibers, plastic fibers, glass fibers, Kevlar fibers, asbestos fibers, cellulose fibers, mineral fibers, high temperature fibers and chips, e.g. inorganic non-metallic chips such as graphite chips and Al 2 O 3 chips and metal chips such as iron chips, heavy components such as barite or lead or lead-containing mineral, and hydrogen-rich components such as hollow water-filled particles. When the composite material is based on Portland cement, i.e. contains at least 20% by weight of Portland cement particles as particles B, sand and / or stone as the only additional pieces lead to important new mortar and concrete composite materials.

Important composite materials of the present invention include materials in which the particles A are silica dust particles having a specific surface area of about 50,000 to 2,000,000 cm 2 / g, especially about 250,000 cm 2 / g, and the particles of the compound. B comprise at least 50% by weight of Portland cement. In these composite materials, the dispersant is preferably a power softener for concrete in such an amount that it results in the dispersing effect described above.

In accordance with the principles described above, the composite material for preparing the subject of the invention has a very low ratio between water and cement and possibly other particles B + silica dust, this ratio being 0.12-0.30 by weight, preferably 0.12-0.20 by weight, and silica dust may be present in an amount of about 0.1 to 50% by volume, preferably 5 to 50% by volume, especially 10 to 30% by volume, based on the total volume of the particles A + B.

According to a particular object of the invention, the composite material is packaged and delivered as a dry powder, whereby the addition of a liquid, typically water, is carried out at the place of use. In this case, the dispersant is present in the dry state in the composite material. This type of composite material according to the invention has the advantage that the composite material can be accurately weighed and mixed by the manufacturer, so that the end user only needs to add the indicated amount of liquid and perform the final mixing according to the instructions, for example as described in International Patent Application No. PCT / DK79 / 00047 in Example 11.

The invention also relates to a method of manufacturing a shaped body, which method is defined in the appended claim 37.

52 7 2 3 0 7

It should be noted that said low stress field determines the amount of dispersant used and does not necessarily mean that the process is actually performed with a low stress field. However, the fact that it can be performed with a low stress field constitutes an important advantage of the process, and suitable low 2 stress fields (suitably less than 5 kg / cm and 2 more preferably less than 100 g / cm) used to form the mass are: gravity acting on the mass , such as self-spreading of the cast soft mass, or inertial forces acting on the mass, such as in centrifugal casting, or contact forces, such as compression, rolling or extrusion, or two or more of the above-mentioned forces acting simultaneously, such as combined vibration and compression. Vibration forces in the frequency range of 0.1 to 10 Hz may also be used to form the mass, the vibration forces being of the type described above, such as those provided by a mechanical or hydraulic vibrator, or such vibration forces may be combined with non-vibration forces such as combined vibration and compression.

For most practical purposes, liquid water is used in the process, and the dispersant is often added together with water, so that in fact an aqueous dispersant solution is added, but within the scope of the invention water can be added separately from the dispersant solution, combining the dispersant with water in the mixing process. It is characteristic that a mixture according to the above definition is "dry" in nature in the mixing step until it becomes a viscous plastic mass, this "dryness" being due to the low liquid content.

The manufacturing technique used to make the moldings according to the invention must, of course, be adapted to the type of composite material in question and to the type of mold in question. However, there are some general guidelines:

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53 7 2 3 0 7 1) The matrix powders (particles A and B) should preferably be present as well dispersed as possible before mixing with each other. If the dispersion in the dry state is unsatisfactory, i.e. if the particles A have accumulated, some kind of dispersion treatment, such as grinding, can be used.

2) Mixing must be ensured by solid particles A

and B homogeneous mutual distribution. This can be accomplished by dry mixing or wet mixing, with the premixed liquid and either particles A or particles B being mixed with the remaining particle type in question. The mixing step can be performed with or without additives.

3) The addition of liquid to either the dry-mixed powder (particles A + B) or either to particles A or particles B in the case of premixing a wet slurry as mentioned in 2) can be carried out either by adding the powder to the liquid (suitably with strong mechanical stirring) or by adding liquid into a powder mass (suitably by strong mechanical kneading). What of these methods should be used is essentially a matter of experience. At present, however, it is believed that in preparing a relatively flowable mass from a well-dispersed powder, the easiest method is to perform mixing by adding a highly dispersible powder to the agitated liquid to avoid liquid between particles, which could occur in the opposite process if small amounts of liquid are added to the powder. On the other hand, if the poorly dispersed very fine powder is added to the agitated liquid, the powder will not be satisfactorily dispersed by the agitating forces, even if a dispersant is added. In this case, the addition of a liquid to the powder while vigorously kneading is recommended, because kneading together with a dispersant may result in a considerable dispersing effect. In the examples (which are mainly based on Portland cement + silica dust), a method has been used in which liquid is added to the powder while kneading / mixing (with a relatively modest shear force of about 100-1000 g / cm 2). For most fluids (mortar and concrete with a water / (cement + silica) ratio of 0.18-0.20 by weight), it is believed that the opposite technique could just as well have been used- For stiffer masses (pastes for extrusion containing fibers and in which the water / (cement + silica) ratio by weight of 0.13 to 0.15) is believed, however, that the opposite technique would not have worked at all; in these cases, an important part of the mixing took place in an extruder where 2 strong kneading took place (in the range of 1 kg / cm).

4) The dispersant is not necessarily added to the liquid as a solution (it can be added as a powder or mixed in a dry state together with particles A and B). In some systems, it is preferred to moisten the surface of the particles with a portion of the liquid prior to the addition of the dispersant-containing solution, as recommended in the prior art for power-softened Portland cement suspensions. This was also done in the cement silica tests described in the examples of International Patent Application No. PCT / DK79 / 00047, with the exception of Example 11. It is worth noting that the mixing time of a very dense water mixture can increase decisively compared to conventional mixing. This was particularly the case for relatively solid mixtures (extruded paste with a water / (cement + silica dust) ratio of 0.13-0.15, cf. Example 2 of International Patent Application PCT / DK79 / 00047), as well as for medium-solid mixtures (water / (cement + silica dust) ratio 0.15-0.16, compare Examples 3 and 9 of International Patent Application No. PCT / DK79 / 00047, which required a mixing time of approximately 15 minutes and 5 minutes, respectively, to change the consistency from almost dry to moist and liquid, respectively. Concrete with a water / (cement + silica dust) ratio of 0.18 also had a longer mixing time, but this was not as clear il 55 72307 as for systems with a very low water / powder ratio. local transport to and between the surfaces of tightly packed solid particles is a time consuming process (this transport is more difficult the smaller the i water / powder ratio is). The consistency of the material is very sensitive to the amount of liquid. Thus, very small additional amounts of liquid can change the consistency from a solid paste to an easily flowable form. In a power-softened cement-silica mixture, this change can be achieved by changing the water / (cement + silica dust) ratio from 0.14 to 0.18.

The addition of a dispersant as a dry powder to a dry mix before mixing with water appears to be an equally valuable way of preparing the casting composition of the invention. This was demonstrated in Example 11 of International Patent Application No. PCT / DK79 / 00047, where this method was used, resulting in a mortar having substantially the same fluidity and nature as that made from almost the same components but mixed as described above, with the dispersant being added as a solution to the pre-moistened mixture. (compare Example 9, Mixed No. 1 of International Patent Application No. PCT / DK79 / 00047).

In each particular system, there is a level at which the system is impregnated with a power softener and exceeding which by further adding a power softener does not produce any additional effect. This saturation point increases with decreasing water / (cement + silica dust) ratio. Above this level, the material is not sensitive to the amount of dispersant. ' 5. The addition of pieces C and possibly D can be carried out at any stage of the operation, such as during dry mixing or after wet mixing, etc.

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In specific cases, the recommended technique to use depends on the nature of paragraphs C and D and is a matter of experience. In the case of concrete and mortar, it is important to ensure a relatively tight packaging of the added sand and stone in order to ensure that a relatively small gap is filled with the dense binder matrix according to the invention. When fine fibers are added, conventional techniques such as vibration / mixing, stirring, and mixing by kneading can be used. By adding continuous fibers or filaments or pre-arranged fibers, such as fibrous webs or fabrics, according to the prior art, a valuable fiber orientation or fiber arrangement can be achieved. It is very common to use the same technique to incorporate additional bodies into the matrix of the invention as to known matrices, but due to the substantial lack of interparticle locking surface forces, it is generally easier to achieve effective incorporation.

6. Drainage, as well as compression, can be achieved with the low stress fields mentioned above. The new-type material is suitable for transport by pumping due to the substantial absence of leakage and the viscous nature of the pulp. However, since the casting mass consists of a particulate material with virtually no bonding forces between the individual particles, vibration, and in particular high-frequency vibration, can greatly promote casting, since the mutual displacement of adjacent particles due to vibration greatly facilitates flow.

7. The curing of the material according to the invention differs less from the curing of the corresponding articles based on tightly packed matrices in two respects:

First, because the structure is more tightly packed, curing is faster (strong at an early stage). Second, curing can be affected by a relatively large amount of dispersant, which is necessary to achieve a particular structure. In Portland-cement-silica-Mighty systems, rapid strength was achieved, but a moderate retardation of curing (4-8 hours) could be observed. In these Portland Cement-Silica-Mighty systems, it could be shown, as predicted by the calcium silicate dihydrate structure formed, that excellent quality could be achieved by curing at about 20 ° C, 80 ° C and 200 ° C (autoclave), which means that the new matrix is useful for conventional low temperature curing, thermosetting and autoclaving. Thermal curing (which in normal concrete results in slightly worse strength than low temperature curing) is probably the most promising curing technique for the material of the present invention.

As described above, the volume of liquid added to the process is preferably such that substantially no liquid escapes from the pulp during the molding process, resulting in several advantages over known methods in which liquid, typically water, is removed from the pulp during the molding process, typically by some sort of filter pressing operation.

Although the process of the invention can be said to comprise a completely new technology, it can also be considered a valuable variation of an existing technology. For example, when fiber cement products are made according to the magnesium process, shaping (from dilute cement / fiber / aqueous solution) is performed by rolling, while removing water by suction. By adding very fine particles as well as very large amounts of dispersants to the pulp to be treated according to the principles of the present invention, these known technologies can be modified to produce, extruded or rolled at a molding pressure of up to 100 kg / cm, (even denser) 58 72307 material a viscous / plastic mass that already has a final low water content so that no water or substantially no water is removed from the mass during the molding process, and as a result no suction arrangement is required.

As indicated above, the additional pieces D (such as pieces C and to some extent the pieces B) can be added at different stages of the process, and these additional pieces D are of different types, as described in detail above, with the only limitation being that some additional piece types such as reinforcing bars or yarns in prestressed concrete can only be included in the casting stage and not in the earlier stage.

Unique improved possibilities in embedded, especially underwater construction include pouring a cement paste, mortar or concrete of the type of the present invention as a cohesive mass into a liquid, especially seawater in a port or lake, allowing the mass to displace part of the liquid and form as a cohesive mass.

Other possibilities to use the excellent formability properties of a viscous or plastic mass include shaping the articles by spraying, painting or brushing to form layers on other articles, or forming the article in layers, simply injecting or applying the mass layer to the surface and shaping the mass according to the surface shape. The centrifugal casting technique is another attractive molding method that is practical in connection with the process of the present invention.

In the same way as described in International Patent Application No. PCT / DK79 / 00047, the articles of the present invention can be further subjected to impregnation in order to further increase their strength and to improve their properties. The preferred materials and methods for performing impregnation are the same as those described in International Patent Application No. PCT / DK79 / 00047.

When the particles A are to be tightly packed in the materials of the present invention, they are preferably in the order of 200 A to about 0.5 μm.

When the particles A used in the examples were SiO 2 particles formed from the vapor phase (in the production of silicon metal in an electric furnace), other very fine particles containing SiO 2 can also be used, especially those mentioned in International Patent Application No. PCT / DK79 / 00047. However, in the context of the present invention, particles formed by growing the vapor phase are preferred.

Casting next to or between surfaces

A new application of concrete, mortar and similar materials has become possible with the high-strength, room-temperature-moldable materials according to the present invention and International Patent Application No. PCT / DK79 / 00047, namely providing the articles with an outer shell and an inner part completely or partially filled with with reinforcing materials (concrete, mortar, paste, etc., reinforced or unreinforced) according to the invention and International Patent Application No. PCT / DK79 / 00047.

This makes it possible to combine the desired special surface properties of articles (chemical, optical, thermal, mechanical, magnetic, etc.) with good general properties (especially high mechanical strength and 60 72307 rigidity) and a simple manufacturing technique (separate shell making and subsequent pouring of concrete or mortar). propagation). This constitutes a particular object of the present invention.

There are numerous advantages and potential advantages in the production of individual hollow shells, which shells are completely or partially filled with materials according to the present invention and International Patent Application No. PCT / DK79 / 00047: 1. The surfaces of the articles (shells) can be made independently of the internal, load the manufacture of the receiving reinforced core, i.e. in environments (in terms of temperature, pressure, external factors, etc.) which are not limited by the requirements of the inner core (extrusion of plastic, manufacture of glass or ceramic shells, etc.).

2. Very large thin-walled pieces with a monolithic reinforced load-bearing core can be made. For example, it is possible to make long pipe lengths with a strong reinforced core in the pipe wall (for example, in lines installed along the seabed where pipes with hollow plastic or other material walls are placed correctly, the spaces are filled with stone and reinforcement, then the pipes are filled with paste or mortar). International Patent Application No. PCT / DK79 / 00047 or by injection according to the present invention).

Other pieces that can be made in this way include ship hulls, large building components, tunnel liners, and the like.

3. Forming work is simpler than in structures where the load-bearing reinforced concrete or mortar is first made in a special mold and then provided with a surface

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72307 with 61 materials. In accordance with the principles of this aspect of the present invention, the surface coatings act as guards.

Structure formation

Curing shrinkage of Portland cement-based DSP matrices__

As it cures, the volume of the cement-based DSP material decreases, as in a conventional cement mix. The volume reduction is considerably greater with the new binder, 2%, when it is 0.5-1% with a conventional cement mix.

This shrinkage may cause unwanted cracks and deformations.

The decrease in volume is due to the fact that water is consumed when the chemical structure is formed and that the reaction products formed have a smaller volume than the components from which they are formed. This causes internal cavities from the cavity and thus internal liquid shocks, which causes tensile stresses in the liquid phase which compress the powder mass. The finer the powder material, the higher the tensile stresses due to the meniscus and thus the contractile forces. When a powder which is 50-100 times finer than cement is used, the shrinkage forces are therefore considerably higher than in a conventional cement mix.

This is known, for example, from the drying of the soil, whereby the volume of the fine clay decreases markedly, while the volume of the coarse sand does not change significantly. The reduction in volume is also highly dependent on the hydration products formed during curing, for example calcium silicate hydrate, in particular their ability to generate internal shrinkage stress as less tightly bound water is transferred for use elsewhere in the hydration process.

Various precautions may be used or designed to reduce or eliminate the volume shrinkage of the binder, to reduce the volume shrinkage of the composite material, and / or to reduce or eliminate potential adverse effects due to the volume shrinkage of the binder, especially cracking.

1) Changing the stress of the liquid-gas and / or liquid-solid interface to reduce the gas-liquid surface tension and / or increasing the contact angle to reduce the shrinkage forces. This can be accomplished by adding surfactants or by changing (raising) the temperature.

2. Add liquid to compensate for the liquid consumed in the chemical reaction. The liquid is added from the outside to the surface of the body or from the inside through channels from an external source or internal sources where the liquid may be present in liquid (e.g. porous sand or rock granules or fibers) or solid form (e.g. ice that subsequently melts) or chemically bound (so that the liquid for example released by chemical or thermal action).

3) The volume of the pore liquid is changed (increased) and thus the chemical wear of the liquid is compensated, for example by heating. (Normally, the thermal volume changes of liquids are considerably greater than those of solids).

4) The volume shrinkage of the composite material is reduced by • using compact packaging of rigid coarse particles - typically sand and rock. Thus, the shrinkage of the mortar and concrete volume is typically reduced by 1/10 compared to pure paste.

5) Internal cracks are made more difficult by a) increasing the energy required to open the cracks, 63 7 2 3 0 7 for example by using sharp-edged sand and stone material and / or fibers and other reinforcements (the inventor has successfully used fine wollastonite fibers, various glass fibers, various glass fibers, -and), b) by increasing the stiffness of the composite material, for example by using tight packing of sand and stone.

(The background of both of these measures can be found in the cracking mechanics, because according to the linear elastic cracking mechanics, the tensile stress is proportional to the square root of the cracking energy multiplied by the modulus of elasticity.) C) adding pieces as guides, as is the case, for example, with large pieces with sharp protruding corners and smooth surfaces.

6. Avoid exposing the shaped body to damaging tensile stresses during curing. This can be achieved, for example, by curing under compressive stress and / or ensuring uniform shrinkage of the body, for example by an appropriate mold structure (including the use of flexible molds of rubber and the like).

7. By providing a more volume-stable chemical structure of the hydration product, for example by adding more calcium-containing very fine particles, such as calcium carbonate particles, as described in the following section "Use of very fine particles to improve the chemical structure of DSP materials".

8. Curing by heat (low pressure steam curing or autoclaving).

64 7 2 3 0 7 9. By using components that consume less water in the hydration process, for example by using cements with a lower than normal C3A content.

10. Using blowing agents, such as aluminum powder, to compensate for the shrinkage by the expansion event simultaneously with the shrinkage. Other typical cementitious blowing agents may also be used.

Use of very fine particles to improve the chemical structure of DSP materials A particularly preferred form of DSP materials comprises particles B and A, where the formation of the structure takes place by partial dissolution in liquid and precipitation, with particles B being more reactive. Typically, particles B are Portland cement (d 5 5 μm) and particles A are silica dust (d 0.1 μm).

The compact DSP structure is shown in Figure 1.

As the structure is formed, a new structure is created that glues together the remaining portion (probably the larger portion) of the original particles, resulting in a structure that remains permanent throughout.

It is desirable to control structure formation both at the colloidal level (i.e., how the adhesive is distributed in the state of the particles A, either uniformly or centered in the vicinity of the particles B) and at the action level (i.e., how the chemical structure is constructed).

As an example, it may be interesting to consider a Portland cement and silica dust system (where average particle sizes are typically 5 μm and 0.1 μm) arranged according to the principles of DSP materials (see Figure 1).

li 65 72307

The solid structure is based on a combined cement-water reaction and a cement-silica reaction in which 1) the substance derived from silica dust forms, to a greater or lesser extent (by dissolution and reaction), part of the resulting solid calcium silicate hydrate structure.

2) The distribution of calcium silicate hydrate between the remaining solid particles is not believed to be uniform, typically having a higher concentration near the surface of the cement particles (where cement is typically the main producer of "structural material"). Thus, it is likely that in certain volumes there is too little calcium silicate hydrate in the spaces between the cement particles and therefore they are prevented from gluing the remaining silica particles into a very dense structure.

3) It is also likely that the distribution of elements in the chemical structure is uneven, typically with a higher concentration of calcium near the surface of the cement particles and an excess of silicon in the calcium silicate hydrate in the state filled with silica dust.

It is desirable to control the structure and structure formation in detail, which means increasing the amount of structure formed in the interstices of the silica particles, even at a greater distance from the cement surface and a high degree of calcium control relative to the calcium silicate hydrate formed. According to the invention, the missing elements (or other desired elements) are added to the fine particles, typically other fine particles.

A natural measure to solve the problem would therefore be to add very fine Portland cement to the fine silica, i.e. to replace 20-80% of the silica with 66 72307 very fine cement, which is typically 2-10 times finer than Portland cement or even more.

This operation significantly reduces the amount of microvolumes filled with silica dust, typically by a factor of 2-10 or even more.

However, this procedure has two drawbacks: 1) very fine reactive cement can cause production difficulties due to too rapid a chemical reaction (solidification effect). (However, this effect is not always undesirable because it can be used for the prescribed rapid binding, which is highly desirable).

2) Very fine reactive particles may dissolve completely as a result of not contributing to the desired ideal particle-based structure.

According to one embodiment of the invention, very fine particles A are used as a source of calcium, which is a much less reactive form than cement, for example by using colloidal calcium carbonate (particle size typically less than 0.5 μm) in a Portland cement-silica system. Calcium carbonate is normally considered to be very sparingly soluble in water and is slowly soluble when the larger granules are used, but due to the large specific surface area (typically 10-1000 m / g) the solubility and dissolution rate increase, making it possible to combine the desire to retain particles within the first few hours. after mixing with water (partially controlled by surfactants) and the desire for moderate reactivity with water and nearby S1O2 particles during curing.

The behavior of the system can be improved / optimized by several measures: 67 72307 1) By geometric equilibrium, i.e. by arranging very small Ca (CO 3) 2 particles (d ^ 0.01 μm) in the spaces between the silica particles.

2) Using very small Ca (CC> 3) 2 ~ particles and thus increasing the solubility of Ca (CC> 3) 2 (according to the thermodynamics of fine particles). The benefit of this effect requires particles that are typically less than 100 Å (diameter), preferably less than 20 Å, for example smaller than particles A.

3) By using means to change the solubility (elevated or reduced temperature) or by changing the chemical composition of the liquid, for example, an aqueous solution of CO 2 greatly increases the solubility of Ca (CO 3) 2.

Thus, one embodiment of the invention comprises incorporating calcium carbonate particles having a size of about 50 Å to 0.5 μm into the A particles. The ratio of calcium carbonate droplet particles to silica dust can vary within wide limits, such as between 1/99 and 99/1.

applications

Due to their very high tightness and mechanical strength, the material provided by this invention is useful in a wide variety of articles, such as thin-walled planar or corrugated sheet or panel, such as sheets or panels similar in shape to known asbestos cement products; tube; management; a refractory liner (e.g., applied as a complete liner) or a component of a refractory liner (such as a building block for a refractory liner); protective coating (for example, to protect other materials from chemical action, such as cheap protective coating applied to steel, for example steel pipes or wires or conventional concrete products, ash for concrete products with a noble surface which is strong, durable and insulates against the environment) protective coatings for masonry, pavements and roads, taking advantage of the same good properties of the new material, and protective coatings for roof tiles or slabs or tanks, roofing materials such as roof tiles or slabs, electrical insulation; deep-seabed structure, machine part, sculpture, tank, in-situ cast oil well wall, or load-bearing element in construction technology, taking advantage of the material's very good strength properties and its resistance to climatic effects, beam, shell or column, typically as reinforced concrete, especially prestressed concrete.

Deep-water seabed structures, such as spherical tanks that can withstand high hydrostatic pressures, require concrete with high strength, good durability, and low permeability.

"Polymers in concrete", ACI Publication SP-40-1973, P 118-48, describes model experiments with small 16-inch diameter spherical bodies made of high quality polymer-impregnated concrete for use in deep water. Complete impregnation was achieved by a complex drying-vacuum gasification-pressure method, which is practically limited to small tanks.

With the materials and methods of this invention, it is now possible to fabricate such structures on a large scale (many meters in diameter) with a similar high quality material using a simple fabrication technique.

· A few examples of the application of DSP materials have already been presented above. Other examples are the following structures that can be made by casting against or between two surfaces: 69 72307

Large electrical insulators today are made of glass or ceramic materials, especially because of the excellent insulating properties of these materials. It is especially important to prevent currents along and in the surface layers. In addition, large insulators need high mechanical strength and a good ability to absorb mechanical energy. This is difficult to achieve with brittle materials such as glass and ceramics, which are difficult to impart "toughness" with reinforcements (due to the fact that they are formed from flowable masses at high temperatures and solidify with fairly large changes in volume). However, according to the present invention, such large electrical insulators can provide high mechanical strength and good ability to absorb mechanical energy by making large hollow sheaths or shells from glass or ceramic, which are then reinforced with reinforced high quality DSP concrete, mortar or paste made by casting a soft mass (injection, etc.); the reinforcement may be pre-placed inside the jacket or shell (large steel bars, etc.) or the reinforcement may be part of the casting mass (e.g. fiber shredding).

It is to be expected that this will make it possible to produce large insulators at a lower cost than those manufactured today and to produce much larger insulators than hitherto known.

Furniture, shelves, doors, etc., which, due to the requirements of appearance, hand feel, cleanability, chemical resistance, etc., require special surface properties combined with good mechanical properties (strength, toughness), can be made of hollow plastic, metal and similar parts ( made, for example, by extrusion), which are filled with a reinforced DSP binder by pouring, injecting, etc.

Safes and other strong containers can be made by filling the cavities of doors and walls with DSP material, pouring soft 70 72307 honey mass (injection, etc.); all or part of the internal reinforcement and hard components (e.g., bauxite rock) may be pre-positioned.

Tanks for radioactive waste in which radioactive waste is poured into the above-mentioned high-strength materials by injecting paste or mortar of DSP material into a tank space in which all or part of the reinforcement, solid radioactive waste and various stiffening agents (e.g. bauxite rock) are placed in front.

Very large sculptures with the desired surface material and which can be inexpensively given the required mechanical strength by filling a thin shell with reinforced mortar or concrete made according to the principles mentioned in the examples above.

Load-bearing structures that require special requirements for the surface material (columns, walls, floors, roof elements, etc.).

Hulls the exterior and interior of which are made of materials with special properties (for example, smooth exterior and heat-insulating interior) in which the required part is filled with reinforced DSP concrete, mortar or paste by injection, etc.

As mentioned above, the separate manufacture of hollow shells that are completely or partially filled with DSP materials has several advantages and potential advantages. In this connection, it should be underlined that, for example, very large thin-walled parts with a monolithically reinforced load-bearing core part can be produced. For example, it is possible to make long pipelines with a monolithically reinforced strong core in the pipe walls (e.g. 71 72307 in the case of seabed pipelines, where pipes with hollow plastic or similar walls are placed in place, the cavity is filled with stone and reinforcement, then the pipes are filled). By injection with DSP paste or mortar). Other structures that can be fabricated in this manner include ship hulls, large parts of the building, tunnel liners, and the like.

The ability to produce concrete, mortar and paste with very high strength and acceptable toughness with a simple casting technique and at room temperature allows the production of parts that are traditionally made of metal. Such parts include, in particular, large load-bearing parts, which are traditionally manufactured as metal castings (covers, hoods, large valves, load-bearing machine parts, etc.) and structural parts (masts, beams and the like).

The high hardness of DSP materials, combined with the fact that they can be easily made tough with fiber reinforcement, allows the materials to be used as grinding or abrasive pieces and wear aggregates, typically made by molding, extruding or pressing soft pulp in the usual manner.

In connection with the claims for this embodiment, it is noted that the phrase "substantially uniform thickness" does not mean limited to special surface layers with a very precisely adjusted thickness. On the contrary, the phrase "substantially uniform thickness" is to be understood only as a difference from structures that can no longer reasonably be considered as surfaces or surface layers, such as a rock structure in which the cavity is filled with DSP mass. The definition that the surface layer or layers must have a structure that differs from the structure of the mass cast against or between the surfaces is intended to indicate that the outer material differs from the inner material used in each case. By no means does 72 7 2 3 0 7 mean that the material used for the outer surface should be of the same type as the material used as the inner material, i.e. contain the same type of matrix.

Also in the case of articles made according to this embodiment of the invention, impregnation of the inner material (and also the outer surface material, if of the general type) may be a preferred treatment to further increase strength and durability, and all other impregnation treatments are performed analogously to impregnation of those materials. between surfaces.

73 72307 Compression molding of DSP

A very advantageous way to manufacture DSP products is to compression-mold DSP materials, the composition of which can vary from plastic to rigid.

This is a fast process / which requires considerably less casting material than conventional casting and which allows the production of significantly higher quality products than is achieved in conventional casting. Provided that the water / powder ratio is significantly lower in compression molding (typically 0.08-0.13 while in the conventional casting of cement / silicon-based articles the ratio is 0.20) and that makes it possible to add more and finer fibers to compression molding compositions ( thus, for example, compression molding of a plastic cement / silica paste is carried out using always 6% by volume of glass fibers with a diameter of 5 μm and a length of 12 mm).

Before compression molding, a semi-finished product is formed which, after compression, becomes the desired product. The semi-finished product is formed by mixing processes and various pretreatments (e.g., injection molding or rolling) to ensure that the semi-finished product has the desired fiber orientation and has the desired starting shape.

The semi-finished product is placed in a press, roller or similar device with the surface of the device facing the front of the product to ensure that the extruded product has the desired shape. Examples are shown in Figures 24-28.

By moving one or more parts of the press, the material is pressed into the cavity, thus forming a desired product having the desired shape.

When removing a mold from the surface of the press, it can be pulled from the press, possibly supporting mechanically stable molds, the requirements for stable molds depending on the mechanical stability of the pressed material, product geometry (size and shape), post-press external influences (gravity, vibrations, etc.). requirements for the stability of the dimensions and shape of the product.

Semi-finished product In this context, the term "semi-finished product" is defined as a piece which is transformed into a compression-molded product by compression.

Semi-finished products can be formed from the components described above (particles, fibers, other components, liquids, etc.) and can be formed into the final product by one of the processes described above (injection molding, rolling, vibratory compression, spraying, etc.) or compression molding (in which case production is carried out).

Semi-finished products can be formed from several sub-components, which are formed into a unitary product in the compression step. Thus, for example, sheet-like products having a particular fiber order can be made by placing thin injection-molded sheets in a suitable and desired direction relative to each other as shown in Figure 25, and desired connecting pieces such as electrical resistors, tubes, cables, clamps, reinforcements, etc., or several others. parts (steel plates, pieces of wood, etc.) can be cast into the product to be manufactured by compression molding as shown in Figures 24-27.

Compression

As mentioned above, the pressing is performed by moving one or more parts of the press relative to the material to be molded and thus pressing the material into the desired shape.

II

Often the mold cavity is closed on all sides and the material is allowed to fill this entire space by pressing the material against the walls of the inelastic mold. This is a compaction process.

75 7 2 3 0 7

In other cases, the compression is performed in cavities that are not completely closed on all sides. An important example of this is an injection molding limited compression process in which material is extruded from a nozzle having a certain cross-sectional area, thus providing a product with a corresponding cross-sectional area, or pattern printing, which is often local compression molding. A very interesting technique is rolling using flexible rolls. The rolling of flexible rolls invented by the present inventor is described in detail in a Danish patent application filed May 1, 1981 to Aktieselskabet Aalborg Portland-Cement-Fabrik, entitled "Valse og fremgangsmide til valsning af et deformerbart materiale" to roll the material to be formed ").

As previously mentioned, the pieces do not normally compress liquid into the environment, which is one of the considerable advantages of DSP casting compound.

However, using drying compression, it is possible to obtain new types of materials consisting of coarse components (large compared to particles B) arranged in a tight package corresponding to what is achieved with the components in question in a compression process (possibly vibratory compression). using the paste.

The sample of coarse components is compressed in one of the following ways: 1) Using a liquid paste (e.g. cement-silica DSP paste with a water / powder ratio of 0.20) which is extruded from the specimens using a filter or dryer in the press (see Figures 15, 16 and 17).

76 72307 2) Using the final amount of less liquid paste — possibly completely without liquid paste, by adding the missing liquid paste by pressing, capillary suction, vacuum suction, or the like in a subsequent process or during compression.

3) Using an amount of liquid paste that corresponds to the ratio in the final product.

In the former case, as mentioned above, the compression is followed by the removal of the liquid. The press device is adapted to dry the removed water without significantly interfering with the pressing process.

Using such a process, it is possible to produce products with good stability immediately after compaction.

Final processing

After compression molding, a specimen having a more or less stable shape is formed. Depending on the stability, different amounts of supports can be used in the part: 1) to place the base support or support in the desired position (the support can be, for example, the floor or shelf), 2) support following the essential parts of the shaped surface to preserve the shape of the finished part; song shapes.

The support parts of the part can be joined in a press, the part of the shaping surface being a mold which, after pressing, follows the part as a form support (molds can be, for example, thin compression-molded metal pieces), or is brought into contact with the part in a separate process after leaving the press.

iT

In many cases, the pressed body is applied to the surface immediately after pressing, primarily to prevent drying during further processing.

77 72307

The surface treatment can be performed using curable compounds to prevent evaporation, which can be accomplished, for example, by brushing, brushing, spraying, etc., or by using an anti-evaporation removable film after removal of the body from the press or by moving the press from the press surfaces.

In many cases, the above-mentioned supports may be utilized in the surface treatment, or the supports may prevent excessive surface treatment, or the support may constitute a surface treatment (e.g., a ceramic surface provided in a press).

Finally, compression can be followed by processes that ensure some solidification of the part - in addition to the solidification caused by the pressure itself. Examples are simultaneous heating (heat transfer from the press or electrically or by microwave heating) or by polymerizing the polymerizable components present in the liquid phase.

According to a particular aspect of the present invention, the formation of a cement / water-based DSP composite material can be retarded relative to the formation of its chemical structure and / or stabilized relative to its shape by freezing the DSP combination or semi-finished product. In this way, the composite material or semi-finished product can be premixed or preformed, respectively, and then transported to the desired application, where the structure formation process can be allowed to continue by melting the product, and possibly further shaping it. This method can be applied more generally to any type of DSP material where structure formation can be delayed, slowed, or stopped by freezing or similar processes. The DSP material used in this process can be preformed in any of the ways set forth in this specification.

78 72 307.

High Stress PSP Molding DSP materials can also be formed at high stresses, typically between 5-100 MPa, in special cases between 100-1000 MPa, and in extreme cases between 1000-10000 MPa.

High stress molding is usually combined with lower stress DSP material preforming, which is typically intended to provide 1) an average shape of the product, and 2) the desired preorganization of particles, fibers, etc. before final high stress molding.

High stress molding can typically be performed by breaking or crushing the pre-arranged particles (e.g., pressure sintering, which is typical of metal particles, or crushing the particles into even finer particles, which is typical of brittle materials).

High stress molding can typically be applied during solidification, for example by hot or cold pressure sintering, or - typically for cementitious products - by forming a structure during hydration.

Forming under high stresses provides denser structures. It is known to mold products under high stress for powder compaction, pressure sintering, etc., but in these known methods it is not easy and in many cases impossible to obtain the desired pre-designed microstructure. Utilizing the construction of a structure according to the technique of the present invention in a highly plastic material at low stress, the desired particle / fiber order can be predetermined, after which the high-voltage treatment can be performed on the pre-arranged structure.

Il 79 72307

High stress molding can be combined with a technique in which a flowable interparticle material is exchanged in a multi-stage infiltration, as described in the section "Washable and strong DSP materials". The exchange can be performed as an intermediate process after the basic structure formation process or before the high-voltage treatment or after the high-voltage treatment.

Products typically manufactured by high-voltage molding include, for example, machine parts that are subjected to high stresses, aircraft and spacecraft parts that are subjected to very high mechanical loads, and other products that are subjected to severe operating conditions, including high-fiber products. are very durable and hard and have high tensile strength and elongation.

A very interesting technique is to combine high stress molding with several pre-arrangement methods described in the section "Compression molding of DSP". Several semi-industrial production methods described in this section can be conveniently combined with post-treatment of a semi-finished product in a high voltage field.

In particular, high-stress DSP molding makes it possible to combine high hardness and wear resistance with high elongation (which is achieved with a high fiber load), which are normally very difficult to combine properties by means of the prior art.

A feature of the present invention can be expressed as a process comprising molding a DSP combination and / or a DSP semi-finished product in a high voltage field, typically 5-100 MPa, in specific cases 100-1000 MPa, and in extreme cases 1000-10000 MPa. Another feature related to the former is that the DSP material, for example a cement-based DSP material, is solidified at a high stress, typically 0-5 MPa, for example by solidifying between press plates. In special cases, solidification can be performed at higher stresses, such as 5-100 MPa, and in very specific cases at stresses between 100-1000 MPa and even between 1000-10000 MPa.

If desired, high stress solidification can be combined with high voltage treatment of the DSP composite material prior to molding, for example by passing, possibly repeatedly, through a narrow gap formed by several roll rooms according to the technique described in European Patent Application No. 80301909.0, published No. 021 682.

Multistage Injection According to a preferred embodiment of the present invention, DSP materials are used for multistage injection into cavities and channels.

In this context, injection refers to the process of filling cavities in solid bodies with a substance, either completely or partially. In certain cases, the term injection in the present sense may also have other purposes (impregnation, filling, etc.).

The purpose of the injection is to partially or completely fill the cavities with a substance that forms a body with a certain structure and properties, a "fill", often as a result of the solidification process.

According to the conventional technique, the injection is often performed by pressing a liquid or readily flowing liquid suspension into the cavity to be filled and then allowing the liquid or suspension to dry or solidify to form a filler having a structure typical of solid injection mass. For example, when grouting cable ducts 11 81 72307 in prestressed concrete, a flowable cement paste is often used. In this case, the filling is a piece of dried cement paste with the properties of this material.

In many cases, a filling with even better properties is desired, for example a cable filling made of a material with a higher volume stability than a cement paste, for example mortar or concrete. However, it is difficult to obtain a mortar or concrete infill if a fine infill is required. Coarse-grained materials such as mortar or cement cannot penetrate hard-to-reach narrow portions of the cavity in the zones between the cable and the channel, where the cable is placed close to the channel wall.

According to the present invention, this problem is solved by injecting in two or more stages with two or more injection materials. Of these, the first filler covers the surfaces and fills even fine hard-to-reach cavities, while the latter injection masses do not have the same ability to penetrate narrow cavities, but can displace the first injection mass from larger, easily accessible cavities.

In this way, it is possible to provide a high-quality filling in the cable ducts in which the volume fraction of large particles (with a maximum particle size of 6-10 mm) is large, but in which the housing and the surrounding filling have the same high quality as the pure cement paste filling. The length of the duct can be, for example, 20-40 meters and the diameter 5-10 cm and the diameter of the cable in the duct 2-3 cm.

The process is a two- or three-stage injection, starting with cement paste and ending with concrete (possibly with sealing tape or mortar), where the latter injection mass replaces some of the previous masses in easily accessible areas, where the coarser mass can pass through Figures 42 and 44-46).

82 72307

Because the new DSP materials are of high quality and provide excellent flow properties (even at high concentrations of coarse sand and stones) and high internal coherence in the casting masses, such a process is highly advantageous using these materials based on tightly packed particles of size 0 , 5 to 100 μm, and the spaces between which are filled with homogeneously arranged and possibly tightly packed very fine particles one or more orders of magnitude smaller than the aforementioned particles.

The basic problem can be illustrated by the simplified structure shown in Figure 42, in which the cavity of a body made of solid material is filled by injection with two different materials.

The reason for using two different materials may be the desire to have certain properties in the cavity (material I may have a specific electrical, chemical, mechanical, thermal, optical or other property) at certain points (e.g. a protective coating between the main filling compound II and the outer solid); the use may be due to process engineering reasons, for example when it is not possible (eg for geometric reasons) to make material II fill area I or when material I facilitates injection of material II (eg by changing conditions in interfacial flow (reducing friction or changing interfacial tension) or preventing injection mass II); separation by preventing the mass from entering the wall material).

The process of the invention first comprises filling the entire cavity (depicted in the total cross-sectional area I + II) with the first material components (material I), and then injecting a second material (material II) which replaces part of material I and provides a filling containing both materials (Figure 42).

83 7 2 3 0 7

The replacement of material I takes place by means of contact forces from the material II (often in the form of pressure or rubbing), preferably also by other forces (e.g. gravity), such as upward injection into the channel with a light mass (I) followed by an injection of mass (II) has a higher density.

The injection according to the present invention requires that a part of the injection mass I which is initially in region II be replaced. In principle, this can be done 1) by pushing the material forward in the direction of injection (which is the usual way) 2) by squeezing the material in area I (which is possible if material I or a substantial part of material I is in the gas phase) 3) by transferring the material to or through it. wherein the cavity is located (e.g., by injecting a body of porous material into the cavities and channels) or by transferring the material to the injection mass II (e.g., by dissolving the injection material I and the injection material II) or 4) using a combination of two or more of the above methods.

As mentioned above, the injection may be performed in several steps, some of which primarily ensure filling, while others may primarily serve to aid performance.

Of immediate interest is the multistage injection of prismatic or near-prismatic cavities, which are characterized by their large dimensions in the longitudinal direction of the sides of the prism compared to the cross-sectional dimensions. In multi-stage injection, the first stage ensures filling of narrow hard-to-reach areas and areas in close proximity to cavity walls, while the final injection stage ensures composite structure in easily accessible, often larger cavity portions.

Two important geometric features must be taken into account when filling the cavity with the particulate material with the highest possible concentration of large particles: the blocking effect and the wall effect.

The blocking effect occurs when the areas to which the larger particles cannot enter for geometric reasons are shown in Figures 37 and 50. According to the principles of the present invention, these areas are filled with a finer material which, according to the particle geometric principle, enters these areas.

The multistage of the present invention, which, as mentioned above, is not limited to DSP materials but is quite generally applicable to injection materials, can be described as a method of filling cavities in solids with a substance (U) containing large particles and a substance (V) containing small particles. particles in such a way that substance V only fills spaces in which substance U cannot enter, by pre-filling all parts of the cavity with substance V and then with substance U, with substance U largely replacing substance V in spaces into which it can penetrate.

Substance U is preferably a Portland cement-based material. According to a further preferred embodiment, substance V is a Portland cement-based material. According to an even more preferred embodiment, substance U is a DSP material and substance V is a DSP material.

li es 72307 The cavities to be filled may be, for example, a duct, a channel or a pipe, or it may be a small circular cavity which is filled in accordance with the above principle "by casting next to or between the surfaces".

The cavities into which the substance is injected may contain, prior to injection, additional pieces such as pre-fitted reinforcement, filler, etc. According to an important embodiment of the invention, the cavity into which the injection is made includes a rod, wire, or cable or a plurality of rods, wires or cables.

Methods for producing DSP materials using a liquid substitute to be replaced later with molding_ The DSP molding process is very well suited for molding improved structures (containing particles, fibers, fabric, etc.) by the desired simple technical arrangements such as mixing, casting, injection molding, spraying, injection molding, injection molding, injection molding by winding fibers, which are typically performed at room temperature, in which case the use of cumbersome occupational safety measures is not necessary. This is disclosed in this application and in International Patent Application No. PCT / DK79 / 00047 for several cement / silica / water systems.

The direct application of DSP technology at high temperatures, for example in the production of metal- or glass-bonded DSPs, or in hazardous conditions, for example in the production of plastic-based DSPs based on monomer / polymer transformation, causes very difficult complications or may be practically impossible.

According to the present invention, it is possible to manufacture such materials by taking advantage of all the advantages of the DSP molding process and by eliminating almost all the complications expected in the manufacture, for example metal- and glass-bonded DSP materials.

This is accomplished by using a liquid excipient in the molding process and replacing the excipient in subsequent processes.

86 72307

It is possible to select an excipient which is very suitable for shaping certain particle structures according to the principles of DSP materials.

The liquid excipient may typically be aqueous, but other liquids may also be selected, for example, if water adversely affects the particulate system, for example by dissolution or chemical reaction, or if other liquid provides better rheological behavior than aqueous liquid.

Also in this embodiment, the molding can be performed by any of the molding principles described in this specification.

The liquid excipient can be removed by evaporation or replacement with another liquid as explained in great detail in the following section: "Highly durable and strong DSP materials". The liquid excipient may be partially or completely retained in the final product, for example, if a certain stiffness is desired in the temporary structure prior to infiltration of the final matrix-forming liquid. A typical example of this is when the liquid excipient is water which reacts with an inorganic binder, for example Portland cement, which is part of the particles B.

For example, the leachable liquid may be a monomer or monomer mixture that polymerizes to form the desired plastic matrix, or it may be water (in which case water cannot be used as a liquid excipient), liquid metal, sulfur, or glass. The infiltrating liquid should preferably wet the surfaces of the particles, which is typically provided by surfactants. Leaching can be aided by creating a vacuum prior to leaching, by pressure or mechanical vibration, il 87 72307, including ultrasonic treatment. For products in which the internal structure itself is not sufficiently rigid to resist the forces of infiltration, it is necessary to use external stabilizing forces, for example by enclosing between the molds during the infiltration process.

The infiltrating fluid can be selected in such a way that it provides the desired physical and chemical properties such as: 1. Mechanical strength and stiffness.

2. Plasticity.

3. Certain optical properties.

4. Certain thermal properties.

5. Certain electrical properties.

6. Certain chemical properties.

Highly durable and strong DSP materials

The use of tightly packed fine fibers or chips in combination with very fine particles that are one or more orders of magnitude smaller than the fiber diameter and have settled in the gaps between the fibers opens up the possibility of producing new high-strength materials with greatly increased durability.

A material having the strongest structure of hitherto known materials is made by adding a high volume concentration of very strong and rigid fine fibers or chips to a plastic matrix, typically a metal such as aluminum, cobalt, or silver or organic material (various types of plastics). Very fine fibers are chips, including Al 2 O 3 chips, graphite chips, iron chips, semi-fibers, silicon carbide chips, and glass fibers. The fiber volume can be up to 50-60% by volume.

The design is based on the fact that the tensile stress of the fiber increases as the dimension of the fiber decreases, which is due to the increasing defectlessness of the fibers 88 72307 (the number of internal defects decreases). To ensure good load transfer, the fibers are added to the plastic matrix. Such materials are typically developed to perform well with high strength / density ratios and high modulus / density ratios, such as those required in spacecraft applications.

The above applies to the superior properties of these combinations in the parallel directions of the fibers. When the materials are in the parallel compression of the fibers, the body breaks as the fibers buckle and the matrix cuts. Due to the mechanical action, which is opposite to the fibers (tension, compression, wear), the body breaks mainly when the matrix is cut. Chemical and thermal resistance, including non-flammability, are largely determined by the mass properties of the matrix material.

In principle, these shortcomings of the above-mentioned types of materials can be reduced, i.e. their properties can be improved by reinforcing and stiffening the matrix. If the matrix material is a mass (i.e. no fibers are obtained), this can be done, for example, by incorporating hard, strong particles, preferably in a high volume concentration.

However, these principles are not immediately applicable to the very high fiber combinations described above because the addition of particles could severely compromise the basic requirement for tightly arranged very fine fibers and chips (unless the particles are at least an order of magnitude smaller than the fiber diameter).

It is known to combine very fine densely shaped particles (size range about 5 μm to 50 Å) with pulp materials used as matrix in fiber combinations.

Il 72307 89

However, it is not known to do this for the fiber combinations in question, which may be due to the great difficulties in preparing such combinations. The conventional technique, based on infiltrating the fiber sequence of the matrix as a liquid, does not allow the addition of very fine particles as a simple particle suspension in liquid because the geometric order of the fibers (typically parallel, tightly packed cylindrical fibers) causes a huge infiltration resistance.

The present invention involves the formation of previously described composite structures using highly tightly packed fine fibers or chips in a solid matrix (typically metal or plastic) in which, as a novelty, the matrix material is reinforced with very fine solid particles, typically 5 μm-50 Ä, in a homogeneously and / or tightly organized matrix without damaging the basic principle of tight order of fibers by mechanically using a simple production process to prevent damage to the fibers.

This has been made possible by the use of the DSP materials product technique described in this application, which is based on molding a particle structure (here fibers and very fine particles) by one of the gentle molding processes typical of DSP materials, using a liquid adjuvant as a molding process. to the second liquid, thus providing a matrix of composite material.

A typical process flow is as follows: 1. Forming a fibrous particle structure using a liquid excipient, for example an aqueous dispersant.

2. Forming may involve mixing a mixture of fibers, very fine particles, and a liquid excipient, and mass 90 72307 by a mechanical cutting process such as rolling, pressing, or injection molding.

3. The molding may include an improved fiber arrangement, typically by fiber winding of a single yarn, mesh or fabric, simultaneously with the addition of an excipient and a slurry containing very fine particles, for example by winding in a slurry. An example of a structure formed in this way is shown in Fig. 5.

4. Forming can be done by a spray technique in which the fibers and the slurry of very fine particles are introduced simultaneously.

5. Several types of additives can be used before and during the molding process to protect the fibers and ensure good wettability and dispersion.

6. The liquid excipient is removed from the pulp, typically removed from the molded body in a gaseous state, which is accomplished by lowering the relative vapor pressure of the excipient in the environment, e.g., by heating, vacuum, or chemical or physical vapor absorption.

7. The excipient may also be replaced by another liquid, for example capillary, by dissolution or by pressure.

8. The space between particles filled by a liquid excipient can be reduced by a chemical reaction between the liquid excipient and the particles.

9. The interparticle spaces are filled with a liquid matrix material by filtration (impregnation), typically as described in this specification and in the specification of International Patent Application No. PCT / DK79 / 00047.

10. The liquid is converted to a solid state by solidification (typically metals and glass) or polymerization (typically 72307 91 polymerizable monomers) which is thermally, chemically, or radioactively controlled.

The new types of high quality materials made possible by this invention can be used, for example, in high-performance rotor blades, and as parts of aircraft and spacecraft.

This part of the invention can be defined as a matrix-containing shaped body comprising fibers having transverse dimensions of less than 100 μm and bodies or particles having a size of about 5 Å to 0.5 μm, homogeneously arranged and preferably substantially tightly packed with fibers. in the preferred embodiments, the volume% of matrix fibers is at least 30. In a preferred embodiment, the volume% of fibers is at least 40, preferably 50-60 and most preferably 70.

According to a particular embodiment, in such shaped bodies, the interparticle substance (I) is a metal or a plastic material.

On the other hand, the invention relates to a method of manufacturing a shaped body, in particular a shaped body comprising a fibrous matrix having any of the above properties, but also more generally a shaped body formed of any DSP matrix, said method comprising using a liquid excipient in a DSP molding process and replacing the excipient with another desired interparticulate in one or more steps.

Fly ash

The preparation of particles A and B and their incorporation into DSP material are aspects of great practical importance for fly ash / cement-based DSP materials. The quality of DSP materials depends largely on the particle geometry and the degree of dispersion of the particles in the fresh material.

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There are several methods for making particles A and particles B, and there are also several methods for making flowable DSP materials. For DSP materials based on Portland cement or the like, very fine particles A are typically produced by precipitation, condensation from the gas phase, or fine grinding of the particles. One important way to get very fine particles A and fine particles B is fly ash from power plants. Fly ash is obtained as a dry powder, which is typically collected from filters. This material can be combined with the cement and any component of the DSP material as a dry powder or mixture containing all or part of the DSP liquids (typically water plus dispersant) or mixed with any additives and / or sand and / or stones and / or fibers (wet or dry).

Fly ash can be improved for incorporation into DSP materials by adjusting the particle size and particle size distribution of the fly ash by grinding and / or separating and / or removing unwanted chemical components.

Grinding can be performed by grinding.

Fly ash useful for incorporation into DSP materials can be separated by methods such as screening, electrofiltration, flotation techniques that utilize gravity and inertia in liquids (wet separation such as sedimentation or centrifugation), or air separation (such as using cyclones). The above methods can be performed in the desired order.

When grate ash is used in DSP materials, its roughness typically corresponds to at least a specific surface area (Blaine) of 5000 2 2 cm / g, in particular at least 7000 cm / g and often at least 2 10000 cm / g. When a fly ash fraction containing fine particles is obtained by a separation technique, the particles are typically

II

93 72307 is substantially spherical, and therefore one embodiment of the present invention comprises a fly ash fraction having the above-mentioned specific surface area with the fly ash particles being substantially spherical.

Fly ash having these properties is a very useful material in the production of DSP materials from cement or cement-type materials. Such fly ash may be shipped or transported by other suitable means, for example by pipeline transport, dry powder, liquid slurry, agglomerated form, compressed cake or other forms known in powder technology.

In general, the preparation of ultrafine particles A and particles B to be combined with DSP materials can be accomplished by disintegrating (finely grinding) larger particles (aggregates) or growing particles from the gas or liquid phase (or often in combination, forming final particles by, for example, precipitation and subsequent refining particle agglomerates).

Particle decomposition can be achieved by mechanical means. One way is to prepare a dispersion in liquid excipients involving one or both of the general principles of a) breaking (crushing, cutting, or grinding) particles in a liquid excipient between two external surfaces, or b) disintegration as a result of abrasion between the particles themselves in the liquid. In both cases, the surfactant helps to reduce the rupture stress of the individual particles and / or to prevent re-aggregation.

Another way to cause particle decomposition is a similar dry process. Typical techniques are ball grinding, colloid grinding, plastic grinding, (roller mill), sand grinding and high speed stone grinding.

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Quite generally, any method known in powder technology can be used for this purpose.

When disintegration and mechanical dispersion take place in a liquid, it is desirable to use highly viscous solutions to provide high shear stress at a moderate degree of shear. Adding a thickener may be helpful.

Certain types of particle grinding methods are used to obtain very fine particles. One method is to grind the material as a source of particles, especially type A particles, together with another material which is not used as the source of particles A. This second auxiliary material prevents re-aggregation of the fine particles A during the grinding and dispersing process. The auxiliary material can either be removed or used in the second step in shaping the desired part. An example is salt grinding, in which a large amount of salt is ground together with the material forming the particles A. The salt is then typically removed by dissolving. Another new method is the grinding of an icy material, in which a premix of the material formed by the particles A (preferably pre-ground) and the liquid excipient used in the grinding is frozen and then further ground in solid form.

Particle comminution and dispersion can be achieved or assisted during the mixing process, transport, and / or molding.

Thus, the fine powder is typically prepared (dispersed) in the liquid used in the subsequent molding process, and also preferably with the dispersing aids used in the subsequent processes.

Dispersion of the particles can take place in connection with mixing in any combination of substances used, for example, li 72307 95 1) very fine particles + liquid 2) very fine particles + liquid + dispersing aid 3) slurry mentioned in 1) or 2) together with particles C with (typically rock and sand) 4) very fine particles + any solid particles (B and / or C) without or with a dispersing aid (the dispersing aid in this case is typically combined with a dry powder).

Dispersion can be provided or aided in its formation during transport, in which case the powder is combined with any other component in pipes, where transport is typically carried out at high pressure.

Dispersion can be provided or assisted during the molding process, for example, by injection molding, rolling, compression, vibratory compaction, ultrasonic assisted compaction, etc.

Especially large shear processes such as injection molding and rolling are useful. But also effective vibration and ultra-sound treatment can help dispersion.

Other principles are to form particles by growing from a gas or liquid state using any of the techniques described in the literature.

The production of very fine particles (particles A) requires several additional steps:

Particle separation is typically used to provide the desired particle size and shape (and in the case of some particles, also to provide particles of the desired type (desired chemical, mineralological, magnetic, etc. structure)).

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Example 1

The materials used in the example were as follows:

White Portland Cement: Specific Area (Blaine) 4380 2 3 cm / g. Density (assumed) 3.15 g / cm.

Silica powder: Fine spherical SiO ~ -containing powder. The specific surface area (determined by the BET technique) is about 250,000 cm / g, corresponding to an average particle diameter of 0.1. Density 3 2.22 g / cm.

Bauxite: Refractory calcined bauxite, 85% Al-O .., 3 3 z · * density 3.32 g / cm for sand 0-4 mm, 3.13 g / cm for stone 4-10 mm.

Il 72307 97

Mighty: A so-called concrete superplasticizer, the sodium salt of a highly condensed naphthalenesulfonic acid / formaldehyde condensate, typically more than 70% of which consists of molecules containing 7 or more naphthalene rings.

3

Density per 1.6 g / cm. Available as either a solid powder or an aqueous solution (42 wt% Mighty, 58 wt% water).

Water: Tap water.

Manufacture of cylindrical concrete specimens from wet concrete mixed with silica powder / cement binder and calcined bauxite sand and stones:

The concrete specimens were made from a single batch of 23 liters with the following composition:

Silica powder: 3200 g

White Portland cement: 16000 g

Bauxite 4-10 mm: 32750 g

Bauxite 0-4 mm: 10900 g

Mighty (powder): 250 g

Water: 2980 g

Blend

The coarse aggregates, cement, and Mighty powder were mixed dry in a 50-liter paddle mixer for 5 minutes. The silica powder was then added and stirring was continued for 10 minutes. Water was added and stirring was continued for about 10 minutes.

Märkäbetöni

The concrete was soft and easy to work with.

Casting At 20 ° C, 6 concrete cylinders with a diameter of 10 cm, a height of 20 cm and 2 covers (40 x 30 x 5 cm) were cast. The test pieces were vibrated for 10-30 98 7 2 3 0 7 seconds on a standard vibrating table (50 Hz).

Drying Immediately after casting, the closed molds of the cylinders were immersed in water at 60 ° C and dried for 5 days. The lids were covered with a plastic film and dried for one day at 60 ° C in air, after which they were immersed in 60 ° C water and dried for 4 days. After drying, the specimens were opened from their molds and stored at 20 ° C in air and about 70% relative humidity until testing (testing was performed within 30 days after heat treatment).

Testing

Density, sound-speed, dynamic modulus of elasticity, compressive strength, and load / strain curve were determined for the six concrete cylinders (load / strain curve was determined for only two specimens).

The table below shows the test results.

Table I

Properties of hardened concrete.

Density Sound Dynamic Compression Static speed modulus of elasticity modulus of elastic modulus 3 2878 kg / m 6150 m / s 109 000 MPa 217.5 MPa 78 000 MPa (standard deviation 6.2 MPa) it 99 7 2 307

Figure 1, graph a, shows the load / elongation ratio for one of the cylinders. The figure shows a comparison of the load / elongation curve (graph c) for a test piece made of normal quality concrete (compressive strength 50.6 MPa) and a piece made of high quality concrete according to International Patent Application No. PCT / DK79 / 00047, made of the same type of high quality binder used here. in the example, but with normal quartz sand and granite rock (graph b, compressive strength 130 MPa).

Example 2

Powder compaction of sand and stone.

The purpose is to evaluate the resistance of several sand and stone materials to decomposition in powder compaction, and in particular to compare natural concrete aggregates with particularly strong and hard materials.

materials

Quartz sand 0.25-1 mm, quartz sand 1-4 mm, crushed granite 4-8 mm, refractory bauxite 0-4 mm, refractory bauxite 4-10 mm, silicon carbide 0.5-2 mm (Qual. 10 / F PS- K Arendal Smeltevaerk A / S, Ejdenhavn, Norway).

100

Comments

The individual particle fractions are relatively evenly distributed with a maximum and minimum grain size (particle size) of 4 or less.

Jauhetiivistys

The individual sand and stone fraction samples were compressed with a uniaxial mold press. The sealing device consisted of a cylindrical mold cylinder open at both ends and two cylindrical pistons (with a mold-cylinder diameter of 30 mm, a powder filling height of about 32 mm and after compression 16-23 mm depending on the type of powder).

The dry materials were loosely poured into the cylinder. Compression was performed on an Instron tester with a constant compaction speed (5 mm / min) and a compression pressure of up to 350 MPa, after which the pressure was reduced by moving the piston in the opposite direction. A force / displacement graph corresponding to sealing and depressurization was plotted.

Score

From the force / displacement plot, sealing pressure comparisons were made for individual materials to obtain identical "density". The results are shown in Table II below.

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Table II

Sealing pressure, MPa, as a function of degree of sealing. The degree of compaction is the ratio between the volume of the particles and the total volume of the powder mass (in other words: 1 - porosity)

Compression Granite Quartz Quartz Bauxite Bauxite Peak degree bidi 4-8 rtm 1-4 mm 0.25-1 imi 4-10 nm 0-2 nm 0.5-2 nm 0.70 16 10 24 36 61 48 0, 75 29 23 42 61 110 82 0.80 59 43 76 95 194 145

Cn note that the compaction pressure to achieve the same tightness is significantly higher for hard materials (bauxite and silicon carbide) than for materials commonly used as concrete admixtures (granite and quartz).

comments:

The powder compaction technique is suitable for comparing particle strength, provided that multiple particle materials or particle compounds have approximately the same particle geometry and provided that the particle size is relatively large compared to the mold cylinder dimensions. These conditions are moderately met in experiments with quartz sand and fine bauxite (in these cases, the particles are dense, round, and small). In the experiments with granite rock and coarse bauxite, the particle / mold ratio was somewhat too high (about 0.2-0.3) to allow a direct comparison of the results of the experiments with quartz sand and fine bauxite. On the other hand, a comparison between the two is justified. It is difficult to compare the results of experiments with silicon carbide with other results because this powder material, unlike all other materials, has very sharp angles.

Example 3

High quality mortar

Two types of mortar mixtures were prepared, each 102 72307 based on poorly alkali sulphate resistant Portland cement, silica powder and Mighty, but using different types of sand, namely refractory bauxite and silicon carbide (Qual. 10 / F PS-K, Arendal Smeltevaerk , Ejdenhavn, Norway). The purpose was to study the mechanical properties of a mortar made of very strong sand, compare the example with Example 2, and the very strong silica / cement binder described in International Patent Application No. PCT / DK79 / 00047. The following general components (per batch) were used in all mixtures:

Silica powder 645 g

Poorly alkaline sulphate resistant Portland cement 2706 g 42% Mighty solution 195 g

The following components were used in the bauxite mortar:

Bauxite 0-4 mm 6104 g

Water (including water in Mighty's solution) 387 g

The following components were used in the mortar containing silicon carbide:

Silicon carbide 5755 g

Water (including water in Mighty solution) 487 g The volume fractions of sand, cement and Mighty used are the same as those used in Example 9 in International Patent Application No. PCT / DK79 / 00047. The amount of water in the mortar with bauxite was also the same as in Example 9 in International Patent Application No. PCT / DK79 / 00047, while the amount of water in the mortar with silicon carbide was considerably higher. This is due to the fact that

II

103 72307 SiC sand is very sharp angled and therefore requires a more easily flowing silica / cement paste and / or a larger amount (volume) of paste.

Two batches of each type of mortar were prepared, one with the composition described above and the other batch double in size.

Mixing and casting

Mixing was performed in a mixing machine with rotary motion using a mixing paddle. The following procedure was followed for mixing: 1) Dry mix sand, cement + aggregate for 5 minutes.

2) Add most of the amount of water that does not form part of the concrete plasticizer solution. About 50 ml of water is left for later use as rinsing water. Continue stirring for 5 minutes.

3) Add the concrete plasticizer solution and then rinse the container with the above 50 ml of water to ensure that all the concrete plasticizer has been added to the mixture. Stir for about 10 minutes.

Mortar mixtures behaved like highly viscous liquids and were cast into cylindrical molds (height 20 cm, diameter 10 cm) in a standard vibrating table (50 Hz). The casting time was about 1 minute. The test pieces (in closed molds) were dried in water at 80 ° C for 4 days.

Testing Density, speed of sound, dynamic modulus of elasticity, compressive strength, and load / strain plot were determined. The compressive strength and load / elongation curve were determined in a 500 ton hydraulic press using a load change rate of 0.5 MPa 72307 104 per second. The results obtained are shown in Table III:

Table III

Properties of dry mortar as assessed on the basis of measurements of a cylindrical specimen (height 20 cm, diameter 10 cm)

Bauxite- Silicon carbide mortar

Density (kg / cm3) 2853 (6) x) 2640 (6) x) Speed of sound m / s 6449 (6) X ^ 6443 (6) X ^

Dynamic elastic. .

module MPa 118600 (6) X '109600 (6) *'

Compressive strength and its standard deviation (MPa) 248.0 SD 7.7 184.3 SD 5.9 (6) x (4) x Ä) = number of tests

Load / strain measurements were performed on two specimens from each series. The specimens were loaded with a load corresponding to about 60% of the fracture load and then the load was stopped, after which they were reloaded until fracture without determining the relationship between load and elongation. Some of the samples were loaded and then relieved several times.

The load / strain curve for the bauxite mortar was a virtually straight line over the entire measuring range (0-150 or 160 MPa) with a slope (secant) corresponding to an elastic modulus of 84300 MPa. With repeated loading and unloading, only slight hysteresis was observed.

The load / elongation curves for a mortar with silicon carbide (measuring range 0-100 MPa) flexed somewhat with an initial slope corresponding to an elastic modulus of 86000 MPa and an elastic modulus of 100 MPa at a pressure of 72000 MPa. With repeated loading of 100/120/140/160 MPa, the silicon carbide test piece showed significant hysteresis, indicating a deterioration of the internal structure.

1 05 72307

The compressive strength of mortars with bauxite was not significantly affected by preloading at 150-160 MPa, while the strength of a mortar with silicon carbide was significantly lower on samples previously loaded.

Compressive strength values for preloaded specimens made of silicon carbide mortar are therefore not included in the results in Table IV.

Review of results

It should be noted that mortar with bauxite sand is very strong and rigid and has a compressive strength of 248 MPa (the maximum value for two of the specimens was 254.2 MPa corresponding to a load of more than 200 tons). The fracture progressed largely through the bauxite sand, demonstrating the ability to produce even stronger mortar using even stronger sand materials.

The compressive strength of a mortar containing silicon carbide was significantly lower (184.3 MPa) and not much higher than that of the corresponding quartz sand mortar (160-179 MPa, see International Patent Application No. PCT / DK79 / 00047, Example 9), which may seem strange in that silicon carbide itself is very hard and strong. The reason is undoubtedly that significantly more water is used for the silicon carbide mortar than for the bauxite mortar and the quartz sand mortar referred to in International Patent Application No. PCT / DK79 / 00047. As a result, there is a much weaker binder. The water / powder ratio (total water to cement + silica weight fraction) was 0.149 for bauxite or quartz mortars and 0.179 for silicon carbide mortar. The fracture progressed largely outside the silicon carbide particles. This, compared to the bent load / strain curve and high hysteresis, is typical of brittle materials where the particles are considerably stronger than the matrix) indicates the possibility of providing significantly higher strength by improving the matrix. This can be achieved by lowering the water / powder ratio to, for example, 0.13-0.15, which is possible by using somewhat higher silicon carbide sand and / or a larger amount of cement and silica.

In addition, 16 cylinders of bauxite mortar were made, having the same composition and using the same technique as above, except that the bauxite was from the previous charge.

The purpose was to study several mechanical properties.

Initially, density, sound rate, and dynamic modulus of elasticity were determined for all 16 bodies. The tensile strength was determined as a guide for the two test pieces.

The results are shown below.

Density 2857 kg / m ^ Speed of sound 6153 m / s

Dynamic modulus of elasticity 108 200 MPa

Compressive strength 261.1 MPa 268.1 MPa

Review of test results

The density was found to be the same as above, while the sound speed and dynamic modulus of elasticity were somewhat lower. The reason for this is unknown, but it is believed to be due to errors in determining the time taken by the sound pulse (either in the experiment on page 65 or in the experiment above).

The strengths were slightly higher than above. The highest value of 268.1 2 MPa corresponds to a load of 214.6 tons and a pressure of 2732 kg / cm. Example 4

High quality bauxite mortar

The bauxite mortar was prepared with the same composition and using the same technique as mentioned in Example 3, except as follows: 72307 107 1) the bauxite was from a larger batch, 2) the batch size was twice as large as in Example 3, and 3) the test pieces were allowed to stand for a few days to half a year. after heat treatment (four days at 80 ° C) at 20 ° C and 70% relative humidity.

Four cylinders (height 20 cm, diameter 10 cm) were cast from each of the four batches.

Testing Density, speed of sound, dynamic modulus of elasticity and load / strain plot were determined using the technique described in Example 3.

The results are shown in Table IV below.

Table IV

Properties of dried bauxite mortar based on measurements made on cylindrical specimens (height 20 cm, diameter 10 cm).

Density kg / m3 2857 SD 8 (16) Speed of sound m / s 6153 SD 36 (16)

Dynamic elastic modulus MPa 108156 SD 1426 (16)

Compressive strength MPa 268.3 SD 7.5 (14)

The load / elongation curve is shown in Figure 14 together with a similar graph for ordinary concrete, which is considered to be of very high quality (compressive strength 72 MPa).

It is seen that the compressive strength (270 MPa) of bauxite-cement-mortar is about four times higher than that of traditional high-quality concrete and the modulus of elasticity (curve slope) is about twice as high.

108 7 2 3 0 7

The compressive strength of one test piece was 282.7 MPa and the density 3 2 2861 kg / m, which corresponds to a load / density ratio of 98812 m / s.

The load on the cylinder corresponds to the base load of a 10076 meter high prism made of material.

(For the sake of comparison, it can be mentioned that the yield load of high-quality structural steel (400 MPa) corresponds to a base load of 5200 m high prism).

pictures:

Figures 1, 2, 3, 4 and 5 are enlarged sectional views showing a plurality of DSP systems containing tightly packed pieces, Figure 3 is an enlarged fragmentary sectional view showing a DSP system containing tightly packed compressed pieces, Figures 6 and 7 are enlarged cross-sectional views showing the behavior of cement particles in normal concrete, Fig. 8 is a further enlarged cross-sectional view showing cement particles in a DSP, Fig. 9 is an enlarged cross-sectional view showing the attachment of reinforcing fibers to a DSP matrix, Fig. 10 is a cross-sectional view the internal cohesiveness of the paste and its resistance to non-leaving flowing water, Fig. 11 is a cross-sectional view showing the use of DSP in practice to repair a concrete structure under flowing water that is otherwise difficult to repair, Fig. 12 is a cross-sectional view showing the use of DSP in practice for concrete wall repair Fig. 13 is a cross-sectional view showing the utilization of the good flow properties of the DSP in the manufacture of an internal DSP coating for curved pipes, 109 7 2 3 0 7 , for high strength and refractory bauxite containing DSP, respectively, Figures 15-17 are cross-sectional views showing drying compression, Figure 18 is a perspective view showing the manufacture of a panel-shaped body, which body may be further molded, Figures 19 and 20 are perspective views, Fig. 21 is a perspective view showing the use of injection molding in the manufacture of electrical components encapsulated with DSP, Figs. 22 and 23 are sectional views showing the use of DSP as a plastic material in compression molding, Fig. 24 is a perspective view showing the manufacture of panel-shaped reinforced products, for example wall or roof elements, by superimposing rolled DSP panels, Fig. 25 is a perspective view showing the manufacture of a sandwich element from two fiber-reinforced rolled sheets with fibers in different layers facing each other, Fig. 26 is a perspective view showing the principle of making a panel-shaped piece from two panels with sanitary installations or the like placed between them; Fig. 27 is a perspective view showing a lower element of a similar element to Fig. 26 but with piping for underfloor heating or electrical installation; a perspective view showing the mass production of tiles, bricks, or the like made of DSP board.

References are indicated in the drawings, where like numerals generally refer to like parts.

In Figure 1, which shows a typical DSP matrix structure 10, 12 denotes substantially tightly packed particles B, e.g. Portland cement particles, and 14 110 72307 denotes experimentally organized and preferably tightly packed particles A, e.g. silica powder particles which are homogeneous. dispersed in water by means of a concrete superplasticizer, or a cohesive homogeneous structure formed of particles and a solid interparticulate material formed by a chemical reaction between solutes from cement particles.

The system shown in Figure 1 is typically provided by gentle mechanical means, for example by shear or vibration, or simply under the influence of gravity.

In Figure 2, the particles B (12) comprise larger particles and smaller particles with gaps between them.

The system of Figure 2 is typically provided using the same means as described in connection with Figure 1.

However, in Figures 1 and 21 14 may also mean very fine particles homogeneously organized by the surfactant in the manufacturing process of the liquid DSP system of the invention, but now surrounded by the interparticulate material, which is not the same as the liquid by which the particles is arranged and imported by exchanging the original liquid by filtration.

In Figure 3, the compressible bodies 12, for example polystyrene beads, form partially tightly packed particles B, and homogeneously arranged or tightly packed particles A, typically rigid small particles surrounded by an interparticulate material, fill the gaps between the tightly packed gaseous material B. However, Figure 3 shows a case where the bodies 12 are compressible bodies and larger in size than the particles B, and 14 is solidified in a DSP paste which itself comprises substantially tightly packed particles B and homo- il 1 1 72307 genetically arranged and preferably tightly packed particles. A and interparticulate matter in the interparticle B openings, the structure of the DSP paste being therefore as shown in Figures 1 or 2.

In Figure 4, the fibers or elongate particles 12 form tightly packed bodies B, and homogeneously arranged and preferably tightly packed particles A in the interparticulate material fill the gaps between the tightly packed bodies B. In this case, the tight packing of the pieces B refers to the tight packing, which is achieved by simple mixing and casting with a maximum fiber load, which is limited only by the mixing and molding process. Also in this case, the interparticle substance may be a substance not different from the liquid by which the particles are arranged, the interparticle liquid now present being a substance introduced by exchanging the original liquid by filtration.

In Figure 5, the tightly packed fibers or elongate bodies 12 show the tight packing of the particles B, suggesting the most efficient way to provide a tight packing of compression towers: co-location of the elongate particles or fibers in the homogeneously arranged and preferably tightly packed particles. This structure is achieved, for example, by twisting the filaments of the fibers 12 into a slurry of particles A homogeneously dispersed and preferably tightly packed. The structure shown in Figure 5 is a typical desired structure in a very high quality and very fibrous load and wear resistant material in which the interparticulate liquid A, which are e.g. very fine metal particles, has been replaced by filtration with a strong interparticulate material, e.g. metal or polymer.

72307 112

In Figure 6, the Portland cement particles 16 form an open fluffy structure in the liquid phase in the presence of a surfactant.

Figure 7 shows how, in such a system, the cement particles tend to sediment when the flocculation tendency is removed by a plasticizer.

Figure 8 shows, further enlarged, a DSP paste system, for example a cement / very fine silica system with a plasticizer, in which the gaps between the cement particles 12 are filled with very fine silica particles 18 which are substantially tightly packed in suspension. 20 denotes an interparticle substance, in this case, for example, a superplasticizer solution. In such a system, the tendency for particles to sediment is minimized due to the very slow water flow surrounding very fine particles according to classical hydrodynamics.

Figure 9 shows a fine reinforcing fiber 22 attached to a DSP matrix 10, for example a cement-based DSP matrix. By using such a cement-based DSP matrix instead of an ordinary cement paste, the mechanical adhesion of the reinforcement increases even more than the strength, the addition being one or more orders of magnitude. Therefore, the "roughness" or "waveform" of the fiber necessary to provide "mechanical attachment" of the fiber to the matrix has been reduced by one or two orders of magnitude, which also means that it is possible to provide mechanical attachment in the DSP matrix of fibers that are one or two orders of magnitude smaller than the smallest fibers that can be mechanically attached to ordinary cement paste.

Figure 10 shows the surprising internal coherence of fresh liquid paste into a plastic cement-based DSP mortar 24 subjected to vibration (50 Hz to 10 s) on a load-bearing glass plate 26 and then held under running tap water 72307 113 (flow rate about 4 liters per minute). In this demonstration, the mortar is typically kept under running water for 2-30 minutes without any visible flushing out of the components. The mortar was prepared as described in Example 9 of International Patent Application No. PCT / DK79 / 00047.

Figure 11 shows the repair of a bridge structure 28 in flowing water 30 in a river by underwater injection. Between the base structure 34 made of ordinary concrete 36 and the foundation 38, the erosion cavities 40 have exposed the wooden piles 32, posing a risk of serious damage to the piles. The easily flowing cement-based DSP paste 24 was pumped through one drilled hole 42 into the cavity 40. Due to the high density of the DSP, it replaced water in the cavity 40 and rose into the remaining holes 42, completely filling the cavity and holes and forming a new cover at the top of the foundation. The entire casting was carried out underwater as the river flowed over the fresh DSP concrete, which, however, had such a high internal coherence that substantially no rinsing took place.

Figure 12 shows the repair of wall camps 44 in an underwater tunnel in the Gulf. The easily flowing DSP material 24 filled the cavity to be repaired. The cavity had a complex shape and was strongly reinforced with steel reinforcements 46. The DSP material was introduced from one side through the hose 50 and rose to the other side into the concrete wall 36 and filled the cavity between the concrete wall and the frame 48.

Figure 13 shows the casting of a highly wear-resistant inner masonry inside a steel pipe 52 used to transport powder (coal). The plastic tube 54 was filled with sand 56 and placed inside the tube and held in place by supports 58. A steel fiber reinforced DSP material 24 based on Portland cement and refractory bauxite was poured into the tube 52 under weak external vibration and the material filled the space between the steel tube 52 and the plastic tube 54 therein. After the DSP material dried, the sand was removed and the plastic tube was pulled out.

Figure 14 is a load-strain diagram recorded by a compression test. The experiment was performed on cylinders with a diameter of 10 cm and 20 cm high, made of high-grade concrete and DSP mortar, respectively, which always contained 4 mm of refractory bauxite. The DSP material was DENSIT-S and came from Aalborg Portland, Aalborg, Denmark.

The measured compressive strengths were 72 and 270 MPa, respectively.

Figures 15, 16 and 17 show the compaction of DSP concrete or mortar from a vessel 62 from which, as the piston is lowered, excess flowing paste 68 is squeezed out of the mass and flows past the filler 64 through an opening between the piston 66 and the vessel wall 62. In this case (Fig. 16) the filler body is compressed. After compression, the excess paste is removed (further loaded with a piston). The piston is then removed and the filler body expands slightly (elastic compressive resilience), gently pulling the paste 68 into the openings (suction) to form inwardly turned paste / gas interfaces, which, due to surface forces, stabilizes the compacted dried material.

Figure 18 shows the rolling of a plastic DSP material 68 with a pair of rollers 70 made of an elastic material with an intermediate member 72 connected between rollers to form a semi-finished sheet or sheet of DSP material that can be further formed.

Figures 19 and 20 show the molding of such a semi-finished sheet or sheet 74 between the halves 76 of the compression mold (which can themselves be made of DSP material) into a tubular profile 80.

115 72307

Figure 21 shows the injection molding of DSP material. From the die 82 of the extruder, an injection molded strip 84 of DSP material passes supports 86 in which electrical components 88, e.g., resistance components, are connected to a V-shaped injection molded strip. The strip is cut by means of a cutter 90, and the resulting portions 92 are then compressed into components 94 encapsulated in a compression resin 76.

Fig. 22 shows the compression molding of the DSP material 68 between the upper and lower mold portions 96 and 98, and Fig. 23 shows the molding of the large kitchen table / sink element from the DSP material 68 in the large mold 100, 102.

Figure 24 shows the fabrication of a reinforced DSP panel member by sealing fresh plates 110 and 112 made of cement-based DSP on either side of a steel-reinforced grid 108 in a press 104, 106.

Figure 25 shows the manufacture of a sandwich element made of a fiber-reinforced DSP material in which the fibers in the upper component 110 are oriented opposite to the fibers of the lower component 112.

Figures 26 and 27 show the connection of sanitary pipes 114 or heating pipes 116 to a DSP structural element.

In Figure 28, a fresh plate made of cement-based DSP material is cut into bricks or tiles using a 120 mesh cutter.

The objects of the invention are defined in the appended claims.

Claims (51)

A mold body comprising a coherent matrix, which includes A) inorganic solid particles, such as silica, having a size of about 50 A - 0.5 µm or a coherent structure consisting of such particles, and B) solid particles having a size of 0.5 to 100 µm and which are at least one order of magnitude larger than the corresponding particles mentioned under A), or a coherent structure consisting of such particles, wherein particles A are present in an amount of 5-50% by volume calculated on the particles A + B, a surfactant dispersant, and optionally D) inert filler or reinforcing material, which deviate from the particles B and having at least one dimension thereof are at least one order of magnitude larger than the particles A, characterized in that the particles B are tightly packed. wherein the dense gasket is essentially a gasket which corresponds to that which can be obtained by gentle mechanical paver action on a system of geometrically uniform large particles, where reading surface forces does not have any significant effect that the particles A or a coherent structure consisting thereof are homogeneously distributed in the space between the particles B, that the surfactant dispersant is used in an amount sufficient to ensure the homogeneous distribution of the particles A, and that the mold body further comprising, embedded in the matrix, C) compact shaped solid particles of a material, such as refractory bauxite or silicon carbide, having a strength greater than the strength of ordinary sand and stone used in ordinary concrete, typically a strength corresponding to at least one of a following criteria: 1. a piston pressure exceeding 30 MPa at a packing rate of 0.70, over 50 MPa at a packing rate of 0.75 and over 90 MPa at a packing degree of? 0.80, determined by the method described in Example II (on particles of a material having a size ratio between the largest and the smallest particle which does not substantially exceed 4), 2. a compressive strength of a composite material, wherein the particles are enclosed in a specific matrix, exceeding 170 MPa (in the case that a substantial amount of the particles are greater than 4 mm) and 200 MPa (in the case that substantially all the particles are less than 4 mm), determined by the 1, 3 and 4 described, 3. a Mohs hardness (for the material the particles consist of) above 7, and 4. a Knoop impression hardness (for the material the particles consist of) above 800, these particles having a size of 100 µm - 0.1 m, with the following caveats being applied: 1. at least 20% by weight of particles B is Portland cement, and further 2) since particles B does not have a molecular structure that deviates from the molecular structure of particles A, the mold body is selected from the group requested removes a) bodies made by forming in an area of low tension of less than 2 kg than 5 kg / cm, preferably less than 100 g / cm, b) bodies having at least one dimension of at least one meter and a minimum cross section. . 2 incisions of at least 0.1 m, and c) bodies with a complex shape that do not allow the body to be formed by powder compression. 2. Mold body according to claim 1, characterized in that the particles C are tightly packed, the tight seal being essentially one which can be obtained by gentle mechanical actuation of a system of geometrically uniform Large particles, where reading surface forces do not has some significant impact. Molding body according to claim 1 or 2, characterized in that the particles A are tightly packed, or that the coherent structure A is formed of such tightly packed particles. 130 72307 Form body according to any of the preceding claims, characterized in that the additional materials are selected from the group consisting of compact shaped bodies, disc-shaped bodies and elongated bodies. 5. Mold body according to claim 4, characterized in that the additional materials D consist of sand, stone, polystyrene bodies including polystyrene balls, expanded clay, hollow glass bodies including hollow glass balls, expanded slate clay, natural light additives, gas bubbles, metal bars including steel bars , fibers including metal fibers, such as steel fibers, plastic fibers, Kevlar fibers, glass fibers, asbestos fibers, mineral fibers, high temperature fibers, buckles including inorganic non-metallic buckles, such as graphite and Al000 buckles and 'metallic buckles. 6. Mold body according to claim 4 or 5, characterized in that the additional materials D are tightly packed. Mold body according to any of the preceding claims, characterized in that the particles A are particles which cure at partial dissolution in a liquid, chemical reaction in the solution and precipitation of a reaction product. Mold body according to claim 7, characterized in that particles A have a substantially lower reactivity than particles B or substantially no reactivity. Mold body according to any of the preceding claims, characterized in that the particles B comprise at least 50% by weight of Portland cement particles. 1 (13, 72307) Mold body according to any of the preceding claims, characterized in that the surfactant dispersant than used in an amount of 1-4% by weight based on the weight of the particles A + B. Molding body according to any of the preceding claims, characterized in that the surfactant dispersant is a concrete superplasticizer. Mold body according to any of the preceding claims, characterized in that the particles B comprise particles selected from fine sand, fly ash and fine lime. Molding body according to the preceding claims, characterized in that the particles A are silica particles with a specific surface area of about 50,000-2 2,000,000 cm / g. Mold body according to claim 13, characterized in that the particles A are silica dust particles with a specific surface area of about 250,000 cm / g. 15. A molding body according to claim 14, characterized in that the silica dust particles are present in a volume which constitutes about 10-30 volume percent of the total volume of the particles A + B. Mold body according to any of the preceding claims, characterized in that the particles C consist of materials containing strong natural minerals, strong synthetic minerals or strong metals or alloys. Mold body according to Claim 16, characterized in that the particles C consist of one or more of the following components: topaz, lawsonite, diamond, grain, phenacite, spinel, beryll, chrysberyll, tourmaline, granite, andalusite, 32 72307 staurolite, zircon, boron carbide, tungsten carbide. 18. Mold body according to claim 17, characterized in that the particles C consist of refractory bauxite. Mold body according to any of the preceding claims, characterized in that the particles C are present in a volume which is about 10-90% by volume of the total volume of the particles A, B and C. 20. Body according to any of the preceding claims, characterized in that it, as material D, contains reinforcing rods in the form of bars or rods. 21. Body according to claim 20, characterized in that the bars, rods or fibers are biased. 22. Body according to claim 20, characterized in that said additional materials D (fibers, rods or rods) have retained their geometric identity during the forming process. Molding body according to any of the preceding claims, characterized in that it is a sheet or plate with a thin-walled plane or corrugated shape; a wire; a pipe; a refractory liner or component of a refractory liner; a protective coating, such as a protective coating in place, ordinary concrete, masonry, sidewalks and roads; a roofing material, such as a roof tile or roof tile? a shield against radioactive radiation; a seabed structure for use in deep water; a brake pad? an abrasive aggregate; an on-site molded oval well wall; or a supporting element in structures, such as a beam, frame or pillar, typically as reinforced concrete, especially as prestressed concrete; a machine part; or a sculpture. »I 133 72307 Composite material for preparing a mold body according to any one of claims 1-23, which contains A) inorganic particles, such as silica dust, having a size of about 50 Å - 0.5 µm, B) solid particles of the order of 0.5 - 100 µm, which particles are at least one order of magnitude larger than the corresponding ones mentioned under A), wherein the particles A are present in an amount of 5-50% by volume based on the particles A + B, a liquid, and a surfactant dispersant, and optionally D) inert filler or reinforcing material which differs from the particles B and has at least one dimension, so is at least one order of magnitude larger than the particles A, characterized in that the particles B are tightly packed in the composite material so that the particles A are uniformly distributed in space. between the particles B, that the amount of liquid substantially corresponds to the amount required to fill the space between the particles A and B, and that the amount of dispersant is sufficient for to provide the composite material. a liquid-to-plastic consistency in a region of low stress of less than 5 kg / cm, and that the material further contains C) compact shaped solid particles of a material having a strength greater than that of ordinary sand and rock used. in ordinary concrete, typically a strength corresponding to at least one of the following criteria: 1. a piston pressure of over 30 MPa at a packing degree of 0.70, over 50 MPa at a packing degree of 0.75 and over 90 MPa at a packing degree of 0; 80, determined by the method described in Example 2 (on particles of a material having a size ratio between the largest and smallest particle substantially not exceeding 4), 2. a compressive strength of a composite material, wherein the particles are enclosed in a specific matrix, exceeding 134 7 2 3 0 7 170 MPa (in the case that a substantial amount of the particles is greater than 4 mm) and 200 MPa (in the case that substantially all the particles are less than 4 mm), as determined by the method described in Examples 1, 3 and 4, a Mohs hardness (for the mineral particles consisting of) above 7, and 4. a Knoop indentation hardness (for the mineral particles consisting of) above 800, these particles having a size of 100 µm - 0.1 m, with the proviso that at least 20% by weight of particles B are Portland cement particles, or a corresponding material consisting of the same components A, B, C, surfactant dispersant and optionally D and adapted to produce the above-defined composite material . 25. Composite material according to claim 24, characterized in that the particles A are present in a volume which substantially corresponds to dense gasket for filling the space between the densely packed particles B. Composite material according to claim 24 or 25, characterized in that the particles A are silica particles with a specific surface area of about 50,000-2,000,000 cm / g, the particles B comprise at least 50% by weight Portland cement, the liquid is water in a weight ratio of not more than 0.30 based on particles A and B, and the dispersant is a concrete superplasticizer. Composite material according to claim 26, characterized in that the particles A are silica dust particles with a specific surface area of about 250,000 cm / g. Composite material according to any one of claims 24-27, characterized in that the particles C are present in a volume which substantially corresponds to tight packing between the particles C. Composite material according to claim 26 or 27, characterized in that the particles A are present in a volume which is 10-30% by volume of the total volume of the particles A + B. Composite material according to any one of claims 26-29, characterized in that the concrete superplasticizer is an alkali or alkaline earth metal salt of a highly condensed naphthalene-sulfonic acid / formaldehyde condensate, of which typically more Jin 70 percent consists of molecules containing 7 or more naphthalene rings. Composite material according to claim 30, characterized in that the alkali or alkaline earth metal salt is a sodium or calcium salt. Composite material according to claim 30 or 31, characterized in that the amount of superplasticizing material is in the range of 1-4% based on the total weight of Portland cement and silica dust. Composite material according to any one of claims 30 to 32, characterized in that the liquid is water in a weight ratio of water to Portland cement and possibly other particles B plus silica dust of not more than 0.20. Composite material according to any of claims 24-33, characterized in that the particles C consist of materials containing strong natural minerals, strong synthetic minerals or strong metals or alloys. Composite material according to claim 34, characterized in that the particles C consist of one or more of the following components: topaz, lawsonite, diamond, corundum, phenacite, spinel, beryll, chrysberyll, tourmelin, granite, analusite, staurolite, zircon, boron carbide , tungsten carbide. 136 72307 Composite material according to claim 35, characterized in that the particles C consist of refractory bauxite. 37. A process for making a mold according to any one of claims 1-23 or part thereof, characterized by combining A) inorganic solid particles, such as silica, with a size of about 50 µm - 0.5 µm. and B) solid particles of the order of 0.5-100 µm, which particles are at least one order of magnitude larger than the particles mentioned under A), wherein the amount of particles A is 5-50% by volume based on the volume. of the particles A + B, a liquid and a surfactant dispersant, and mechanically mixes the particles A, the liquid and the surfactant dispersant together with particles B and optionally particles C which are compact shaped particles having a size of 100 µm - 0.1 m, and / or inert filler or reinforcing material D, and then, if necessary or desired, combines the resulting mass with particles and / or materials of the above type (B, C, D) with mechanical means to obtain the desired distribution of comp and, finally, cast the resulting mass in the desired shape in a stress range, possibly with incorporation during casting of particles C and / or material D, characterized in that the amount of particles B substantially corresponds to dense packing thereof in the composite material with homogeneously distributed particles. A in the space between the particles B, that the amount of liquid substantially corresponds to the amount required to fill the space between the particles A and B, that the amount of the dispersant is sufficient to impart a liquid to plastic consistency in a low voltage region. at less than 5 kg / cm 2, that the mechanical mixture of the combination comprising particles A and B and optionally additional particles C and / or D is continued until a viscous to plastic mass comprising particles A and B is obtained and any additional lower particles C and / or D, wherein particles A are homogeneously distributed between dense pac Particles C are particles of a material having a strength which exceeds the strength of ordinary sand and stone used in ordinary concrete, typically a strength corresponding to at least one of the following criteria: 1. a piston pressure pi over 30 MPa at a packing rate of 0.70, over 50 MPa at a packing rate of 0.75 and over 90 MPa at a packing rate of 0.80, as determined by the method described in the specification (on particles of a material having a size ratio 2. a compressive strength of a composite material, wherein the particles are enclosed in a specific matrix, exceeding 170 MPa (in the case that a substantial amount of the particles is greater than 4 mm ) and 200 MPa (in case substantially all particles are less than 4 mm), as determined by the method described in the specification, 3. a Mohs hardness (for the mineral particles consists of) above 7, and 4. a Knoop impression hardness (for the mines all the particles consist of over 800, with the proviso that the particles B comprise at least 20% by weight of Portland cement particles. 38. A method according to claim 37, characterized in that the range of stresses which assist in the formation of the pulp mainly depends on gravity forces acting on the pulp, or inertia forces acting on the pulp, or contact forces, or simultaneously the influence of two or more of the pulp. the aforementioned forces. 138 72307 39. A method according to claim 38, characterized in that the range of stresses which mainly effect the formation of the pulp depends on oscillating forces. 6 with a frequency of 0.1-10 Hz, wherein the oscillating forces are of the type mentioned in claim 38 or depend on a combination of such oscillating forces with non-oscillating forces of the type mentioned in claim 38. 40. A method according to claim 37, characterized in that the mold body or part of the mold body is formed by extrusion or rolling with a molding pressure of 2 up to 100 kg / cm. 41. A method according to claim 37, characterized in that the mold body or part of the mold body is formed by spraying, milling or brushing, injecting or applying a layer of the pulp to a surface and adapting the pulp to the shape of the surface. 42. A method according to claim 37, characterized in that the mold body or part of the mold body is formed by centrifugal casting. 43. A method according to claim 37, characterized in that the pulp is poured into a liquid in the form of a continuous mass, where it displaces part of the liquid and is arranged as a continuous mass. 44. A method according to claim 43, characterized in that the liquid is water and the pulp is a paste, mill or concrete for the construction of an underwater structure. 45. Process according to any of claims 37-44, characterized in that the particles A are silica particles having a specific surface area of about 50,000.