DK163298B - SHAPED ARTICLE AND COMPOSITION MATERIAL AND PROCEDURES FOR PRODUCING THEREOF - Google Patents

Description

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GENERAL PRINCIPLES

Tightly packed systems containing homogeneously arranged ultrafine particles, for the sake of brevity hereinafter in the description and claims referred to as DSP, 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, including new types of DSP systems and new materials within previously described types of DSP systems, new techniques for establishing DSP systems and new uses of DSP systems.

10 DSP systems provide hitherto unattainable mechanical qualities, including strength, tightness, and durability, of materials and articles based on such systems, and allow such articles and materials to be established by advantageous novel methods that extend the possibilities of establishing advanced microstructures of construction materials with many different applications.

Briefly, the basic principles of DSP systems include the placement of ultra-fine bodies or particles of size from about. 50 Å to approx. 0.5 μιη in homogeneous arrangement in the voids between substantially densely packed constituents or particles having a size of from approx. 0.5 μα. to approx. 100 μα, which is at least one order of magnitude (1 tierpotens) larger than the respective ultrafine particles. Some important features of DSP systems are contained in the following five points: 1. DSP systems employ known geometric and kinematic principles 25 for the mutual arrangement of bodies, especially particles, in the desired configuration - especially in very close arrangement - in fine particle systems. or bodies which are 1 to 2 orders of magnitude finer than those systems in which it has hitherto been possible to take advantage of known particle geometry strategy. With DSP systems, the problems of locking surface forces between adjacent bodies which have hitherto prevented bodies or particles of colloidal size from being arranged in a desired tight configuration are overcome.

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2. Despite the fine bodies or particles of DSP systems, DSP materials can be formed in a region of substantially low voltage.

This is made possible by the advanced use of dispersants (for example, in the cement system by the sheer amounts (1-4% by weight) of a concrete superplasticizer) up to one order of magnitude larger than that used in the prior art.

3. In the DSP materials, the strength and durability are significantly increased. In addition, the mechanical fixation of reinforcing bodies, for example, incorporated fine fibers, is even more increased than the strength, this increase being one or more orders of magnitude. This is because the roughness and wave configuration dimensions of the reinforcing bodies needed to achieve "mechanical locking" of the reinforcing bodies in the matrix are reduced by 1-2 orders of magnitude.

This allows for "mechanical locking" of fibers which are one 15 to two orders of magnitude finer than the fibers which have hitherto been able to "mechanically lock".

4. The quality of the DSP materials of the present invention (primarily strength and stiffness) can be further enhanced by the incorporation of very strong additional particles (e.g., sand and rock of refractory 20 bauxite for incorporation into Portland cement-based DSP materials) .

5. Typical DSP materials are materials that can be molded from a plastic-to-viscous pulp mass by simple shear deformation without exchanging material with the environment, meaning that no liquid should be removed or pushed out of the pulp during the formation of the dense structure. . This makes it possible to produce high-quality products with a much more complicated shape and size than before - and allows for anchoring of components, especially all types of reinforcing bodies that cannot be satisfactorily (or not at all) used in corresponding 30 high quality matrices made in the traditional way. This aspect of DSP materials also opens up the possibility of new and more advantageous production techniques for known objects.

In this context, the terms "bodies" and "particles" refer to areas with physical boundaries, the term "physical" referring to 3

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for specific properties, for example mechanical, electrical, optical and chemical properties.

STRUCTURE OF DSP MATRIX

Shaped objects containing a DSP matrix can generally be defined as shaped objects containing a coherent matrix, wherein the matrix consists of A) homogeneously arranged bodies or particles of a size of from ca. 50 Å to approx. 0.5 μια, or a coherent structure formed from such homogeneously arranged bodies 10 or particles, and B) tightly packed bodies or particles having a size of approx.

0.5-100 µm, which is at least one order of magnitude larger than the respective particles mentioned under A), or a coherent structure formed from such tightly packed particles, the particles A or the coherent structure formed therefrom, is homogeneously distributed in the spaces between the particles B, and the dense gasket is substantially a gasket similar to that obtainable by the gentle mechanical action of a system of geometrically similar shaped large bodies or particles, where locking surface forces do not has any significant effect, and an interparticle substance (I) in the spaces between the bodies or particles A and B or the structure formed by the bodies or particles A and B.

The bodies or particles A and B are typically solid bodies or particles, but they can also be gas-phase or liquid-phase bodies or particles. Similarly, the interparticle substance I may be solid, 4

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or it may be a gas-phase or liquid-phase substance, provided that when the inter-particle substance of a DSP shaped article is not solid, the necessary "bonding" is provided to maintain the shape of the article by particle-to-particle bonding.

Thus, the intrinsically coherent structure of the matrix of the above-defined DSP objects of the invention may be due to the homogeneously arranged or tightly packed bodies or particles A being combined with each other to form a coherent structure or the above-mentioned solid particles B is combined with each other to form a substantially coherent structure, or that both the ultrafine particles A and the particles B in the shaped articles are each combined with each other to form coherent structures, and / or that the particles A are combined with the particles B to form the cohesive structure. The combination 15 between particles A or between particles B or between particles A and / or particles B may be of any character resulting in a coherent structure. In systems comprising cement particles such as particles B and silica dust particles (as defined below) as particles A, the formation of the cohesive structure results in partial dissolution of the solid particles in the aqueous suspension of which the articles are made, chemical reaction in the solution and precipitation of the reaction product wherein the silica dust is less reactive in this regard than the cement. In this connection, it should be noted that, depending on the identity of particles A and B, other mechanisms causing coherence may also have been responsible for the coherent structure of the matrix, such as e.g. melting, sintering, etc. The aforementioned chemical reaction can take place between Particles A or their dissolved constituents, or between Particles B or their dissolved constituents, or between Particles A and B or between constituents of Particles A and Particles B.

A substantially coherent structure may also be established by solidification of another interparticle substance, for example, by solidifying a melt or liquid such as physical solidification, including solidification of a metal or glass melt, and chemical solidification including polymerization, e.g. to form a plastic substance.

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Molded articles containing a matrix having a substantially coherent structure comprising homogeneously arranged or densely packed solid particles A together with densely packed particles of Portland cement could only be prepared in the prior art by compression in a high stress area , typically at high-pressure powder compression. In contrast, a very interesting group of molded DSP articles comprises molded articles made by molding in a low stress area of less than 5 kg / cm 2, preferably less than 100 g / cm 2, and having a matrix having a substantially coherent structure containing homogeneously arranged or densely packed particles A, or a coherent structure formed from such homogeneously arranged or densely packed particles A, and densely packed particles B, wherein at least 20% by weight of the densely packed particles B are Portland cement particles or a coherent structure formed from such tightly packed particles B. Another way of characterizing the group of shaped DSP articles having homogeneously arranged particles A between tightly packed particles B, of which at least 20% by weight are Portland cement particles, are referring to the dimensions of the object. Such 20 articles having a correspondingly tight gasket between the particles B and at least one dimension of at least 1 m and a minimum cross-section of at least 0.1 m 2 are not believed to have been manufactured in practice by high-pressure powder compression techniques before the invention of DSP systems. Another way of expressing this type of DSP object is by indicating that the object has a complex shape which does not allow it to be produced by powder compression.

A very interesting aspect of the DSP materials is that it is possible to establish structures of the above types with inherently weak particles and themselves weak additional bodies which would have lost their geometric identity (would have been crushed or drastically deformed) by prior art treatment in a high stress area. This allows the establishment of dense structures with materials that have not previously been used for this purpose.

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The principles of tight packing are discussed in detail in the section "PRINCIPLES OF CLOSE PACKAGING".

In the present specification and claims, the terms "ultrafine silica particles" and "silica dust" refer to SiO2-rich particles having a specific surface of approx. 50,000 - 2,000,000 cm 2 / g, in particular approx. 250,000 cm 2 / g. Such an product is produced as a by-product in the manufacture of metallic silicon in electric furnaces and contains particles having a particle size of from about. 50 Å to approx. 0.5 µm, typically in the range of approx.

200 Å to approx. 0.5 μπι.

10 BODIES OR PARTICLES A AND B IN THE DSP MATERIALS

In International Patent Application No. PCT / DK79 / 00047, the particles A and B of the DSP materials are generally referred to as solid particles with particle sizes typically of between 50 Å and 0.5 µm, respectively between 0.5 µm and 100 µm.

The above-mentioned international patent application mainly discloses compact shaped particles, typically relatively hard materials such as Portland cement, lime, fly ash and colloidal silica. However, as particles B are also mentioned weak materials which are easily deformed under pressures below 5 kg / cm 2.

In this specification, the term "bodies" is intended to mean bodies of any shape, including particle shape, elongate shape, plate shape or fiber or continuous fiber or wire shape, and the term "particles" generally refers to compact shaped particles, but may also include angular particles and somewhat flattened and elongated forms which are within the normal definition range of the term "particles". In addition, the term "particles" in connection with the general description of DSP systems of the present invention may be used as a common term instead of "bodies" where the meaning is obvious.

30 The tight seal, as discussed in the "CLOSE PRINCIPLES" section

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Gasket "is related to the geometry of the particles and to the type of packing or molding process.

PRINCIPLES OF CLOSE PACKAGING

Close packing of constituents and particles is essential in connection 5 with DSP systems. By way of example, the essential property of Portland cement-based DSP materials is the tight packing of cement particles, combined with the incorporation of ultrafine particles into the gaps between the cement particles.

In the manufacture of volumetrically stable DSP concrete and mortar, it is also desirable to pack sand and stone as tightly as possible, as the spaces between the aggregates are filled as tightly as possible with dense DSP paste.

This packing is not clearly defined, but depends on the shape of the bodies or particles concerned, on the size distribution and on the compression method.

Impact of particle shape

The packing density depends on the particle shape, so that the more angular, elongated and rough the particles, the lower the density will be.

For Portland cement DSP paste, the large particles 20 (cement) will typically have a cubic-angular shape with moderate packing ability. (The shape of the cement particles depends on the method of production (grinding).

As for packing, spherical cement would be ideal. Such a cement form can be produced by nucleation and growth in the liquid phase. On the other hand, the SiO2-rich ultrafine powder consists of spheres formed by condensation from the gas or liquid phase. The ball shape results in ideal packing properties.

Tightly packed elongated bodies such as fibers will typically be arranged in a much more open structure than compact shaped particles (cf. FIG.

4) unless special precautions are taken (cf. Fig. 5).

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Impact of particle size distribution

The effect of the particle size distribution can be illustrated by considering binary mixtures (large particles and small particles) as opposed to multicomponent mixtures.

5 Close packing of particles dominated by the geometry of the particles (without the influence of surface forces) has been addressed worldwide in the literature dealing with particle technology for various fields, e.g. in "Particulate Technology," Clyde Orr Jr., 1966, The MacMillan Company, New York, and "Principles of Particulate Mechanics," 10 Brown and Richards, 1970 Pergamon Press. Typically, packing of particle systems where surface forces are negligible is independent of the absolute particle size and only dependent on the shape of the particles, the relative size distribution, and the mechanical manner in which the particles are disposed. This means that uniform packing 15 of equal spherical particles results in the same volume fraction of solids content (e.g. 0.52 for cubic packing and 0.74 for hexagonal packing), regardless of the absolute size of the balls.

The density of the package is strongly influenced by the relative particle size distribution, ie. the ratio of the different particle sizes. Thus, Brown and Richards (loc.cit.) Report on classic experiments with binary packages of spherical particles of different sizes, where the volume fraction of solids content increases from approx. 0.63 for packing each of the individual particle size fractions to approx. 0.70 for a mixture of large and small particles with a size ratio of 3.4: 1 and to 0.84 for a mixture of large and small particles in a size ratio of 16: 1. The density of the gasket is also strongly influenced by the mechanical compression method. Simple pressure compression will not normally result in particularly tight packing of particle systems in which the particles retain their geometric identity (i.e., are not substantially crushed or deformed).

Normally, closer packing is achieved by shear deformation, repeated shear deformation or balanced vibration, all under the influence of a small normal pressure to ensure that the repeated deformation eventually results in a more dense structure. Therefore, it is not possible to specify tight gasket expressed in one unequivocal quantity 9

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identity. The "tight gasket" referred to in this specification is to be understood as essentially such a tight gasket which would be obtainable in systems without locking surface forces under the influence of the aforementioned species such as shear deformation and balanced vibration.

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The closest packing is achieved by a high aspect ratio of large to small particles, typically above 20: 1.

For small diameter ratios, the maximum packing density is reduced due to the wall and barrier effect (cf. Figs. 29 and 30), which is given 10 increasing importance by increasing fine particle to coarse particle ratio.

Without the wall and barrier effect, theoretically 100% dense packing in a multicomponent system can be achieved by continuously filling the gaps between the particles with finer particles.

15 Where the ratio of the largest to the smallest particles is limited, for example to ca. 10 ^ - 10 ^ for concrete or cement based DSP with up to 10 mm aggregate and fine cement fraction of 1 μπι, and in the case of DSP, also ultrafine silica particles with an average particle size of approx. In practice, a significant 20 wall and barrier effect occurs if the number of separate particle fractions is more than 3 or 4, which will result in a far from ideal packing.

There does not appear to be any theory that would allow theoretical construction of the grain grading curve that would provide the optimal packing. The solution, therefore, seems to be a compromise between, on the one hand, a pack of few components and of low wall and barrier effect, and on the other hand multicomponent gaskets. In each case, the optimum gasket can be measured by preliminary physical compression tests.

However, some general principles can usually be used:

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1. A tightly packed particle fraction - for example, rounded, compactly shaped fine particles of between 10 and 20 μια. - should be protected against reducing the gasket by ensuring that there is a significant jump in particle size (for both larger and smaller 5 sizes).

2. For ultra-strong cement-based materials, the dense gasket of the reinforcing cement particles should be protected by particle size leaps (both for larger and smaller sizes), for example by using relatively coarse sand 10 on the one hand and ultrafine particles on the other hand. which is significantly finer than the finest fractions of the cement.

3. Where other cement fines or fibers are used, e.g. glass fibers having a diameter of 10 - 20 μια, in cement-based DSP, it is possible to compensate for the relatively large increase in the void percentage of the cement fraction occurring on the surface of these particles or fibers by adding a correspondingly higher proportion of ultrafine particles A.

The close packing of constituents or particles where surface forces are eliminated depends to a large extent on the kinematics of the placement of the bodies. Fibers can e.g. is arranged in what is considered to be tightly packed in the context of the present invention, by 1) a simple mixing and casting technique (cf. Fig. 4), 2) sedimentation (cf. Fig. 31) and 3) filament recovery as illustrated in Fig. . 5. The density or fiber concentration is greatly increasing from 1) via 25 2) to 3). Typical fiber concentration values obtainable by these three methods are 5, 20 and 60% by volume, respectively.

Thus, it is clear that the tight seal is the combined effect of the shape of the particle and the body and the manner in which the particles or bodies are arranged, ie. the kinematics, under conditions 30 where the concentration of particles or bodies is under only negligible influence from surface forces such as in DSP systems with incorporated effective dispersant.

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SURVIVAL OF SURFACE FORCES

An essential part of establishing a DSP system is the overcoming of surface forces between the small particles and bodies to secure the important tight seal.

Thus, for cement-based DSP, the issue of obtaining tight gasket is essentially a matter of overcoming locking surface forces between the cement particles and the ultrafine particles in aqueous dispersion.

For particles of compact rounded shape and held together by surface forces, the forces required to separate two particles in point contact or to cause mutual sliding are proportional to (a) the particle dimension (d) and the surface tension (7 ) F a yd 15 The surface tension 7 is defined as 1) the surface tension between the liquid meniscus and the surrounding fluid (usually air) when the cohesion is caused by the meniscus, or 2) the work needed to create one unit area of new surface by removing plane parallel surfaces from the contact area to infinite distance.

From the assumption that separation and sliding resistance predominates over rolling resistance, the yield stress of a powder (which is proportional to the force acting on a particle divided by the area of the particle) can be expressed as y1 p α yd ^ 25 or in dimensionless form pd - constant 7 where the constant is a function of the geometry of the particle system (relative to particle size, shape and arrangement).

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This qualitative model has played a major role in the choice of strategy for the production of dense, strong, cementitious materials, including DSP, where particle packing has been used as a function of 5 - pd 7 ·

The size pd 10 - 7 is a measure of the extent to which external stresses (p) are capable of overcoming the inner context (expressed by 7 15 -).

d

Ultrafine particles subjected to surface forces are typically packed in a very open structure if the packing takes place under moderate external pressure. This is an example of compression of a particle system with very low dimensionless compression pressure pd> 7 which results in a correspondingly low particle concentration.

25 Closer packing can be achieved by 1) stronger compression, 2) reduction of surface forces, e.g. using surfactants or 3) selection of larger particles.

At very high values of pd 7 30 -

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13, the effect of surface forces is practically overcome, cf., for example, a heap of stones. Here, the particle pack is in principle a matter of particle geometry, particle friction and the way in which the compression is carried out. vibration.

5 Preparation of extremely strong and dense concrete requires a binder consisting of very fine particles arranged in tight packaging. However, under normal circumstances, the combination of small particles, locking surface forces and moderate compression pressure does not allow the production of such a dense structure.

10 According to the DSP principle, the locking effect of surface forces in cement-based materials is virtually completely eliminated by dispersants, providing ideal geometric arrangements for packing small, spherical particles between larger particles to ensure a very dense structure, despite the fact that the 15 small particles packed between the cement particles are approx. 1/100 of the size of normal cement particles (silica dust with an average diameter of 0.1 μία).

Thus, according to the DSP principle, effective dispersants are used to impart conditions on ultrafine particle-based materials under which packing density has become a purely geometric and kinematic problem known from the theory of large particle packing.

According to a particular aspect of the present invention, it is also possible to compress DSP objects in areas of higher voltage, cf. the following section "FORM IN A AREA OF HIGH

VOLTAGE ". By using compression in high voltage areas, it is possible to successfully establish DSP systems based on the smallest particle size in the range specified for the particles A, which is 50 - 200 Å where surface forces (γ) according to the model 30 pd - = constant Ί 14

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will become increasingly important. By correspondingly increasing the compression pressure p, the high level of pd 5 7 characteristic of the conditions under which the surface forces have been overcome can be maintained.

Other methods for arranging fine constituents or particles such as sedimentation may employ similar principles; only the ma-10 thematic models are different. Thus, when settling small fibers, the dense arrangement depends on whether gravity acting on the fiber is able to overcome the surface forces that will fix or lock the settling fiber (such locking or fixation is typically a fixation in an absolute undesirable position not parallel to the other fibers), so that the settling fiber will achieve a desired position substantially parallel to already sedimented fibers (cf. Fig. 31).

FUNCTION OF DISPERSIBILITY IN SYSTEMS WITH PORTLAND CEMENT AND ULTRAPHINE PARTICLES

Dispersion of fine particles by surfactants is generally explained in the literature on colloidal and surface sciences.

The purpose of using a surfactant is to establish such repulsive forces against neighboring particles that repulsive forces 25 are capable of overcoming the mutual attraction caused by London / van der Waals forces and possibly other attractive forces.

Hereby, attempts are made to eliminate locking between the particles and thus ensure sliding of the particles relative to each other, which is absolutely essential for the establishment of tight packing in a low voltage area.

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According to a classical theory, two repulsive mechanisms must normally be taken into account: electrical repulsion caused by the development of an electrically diffuse bilayer in the medium surrounding the particles (cf. DLVO theory) and steric hindrance where particles are prevented from are assembled (for example, prevented from flocculating) due to the presence of adsorbed layers of another compound on their surface.

Such adsorbed layers may be molecules from the medium or they may be surfactant molecules. The physical interaction of the adsorbed molecules as the particles approach each other acts as a barrier to flocculation. It is believed that the steric barrier effect is the dominant factor in cement dispersed in water under the influence of typical concrete super plasticizers, but electrical repulsion is also included in the mechanism as an additional contribution.

Many years of experience show that a pure electrical repulsive effect is not sufficient to prevent flocculation of Portland cement in water (probably due to a high concentration of divalent, I | II {- trivalent counter-ion (Ca and Al) Hardy-Schultz Rule 20 compresses the diffuse bilayer, and perhaps also because of the formation of direct chemical bonds (or bridges). The effective dispersion of ordinary Portland cement in water is likely to depend strongly on the ability of the dispersants to ensure effective steric hindrance.

It is basically much easier to obtain a good dispersion of ultra-fine silica, e.g. with an average size of 0.1 µm, in water than to achieve a similar dispersion of the much coarser Portland cement (typically with an average particle size of 10 μια).

An effective dispersion of colloidal silica in water (without salt content) by pH control (pH typically above 7 or 8) is described in "Surface and Colloid Science", edited by Egon Matijeviec, Ralph K. Iler, 1973, John Wiley & Sons. Practical experience from experiments with the fine silica dust in the working examples (specific surface area approx.

250,000 cmVg) generally shows the same behavior.

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Thus, a mixture of silica dust and tap water in a 1: 1 weight ratio and a 2: 1 weight ratio of silica and 3% aqueous sodium tripolyphosphate solution both result in moderate viscosity slurries which can be easily mixed in low shear mixers or manually. . However, attempts to combine such silica / water systems with Portland cement result in a marked flocculation.

Adding small amounts of light-flow Portland cement / water slurry (typically with a water cement ratio of 1) to a large portion of silica / water slurry of the types and concentrations mentioned above, (f. for example, typically 1 part of cement slurry to 10 parts of silica / water slurry) results in a drastic hardening which makes any further mixing impossible.

This shows that the substances dissolved in the water from the cement destroy the dispersion of ultrafine silica particles. The precise mechanism for the formation of bonds between the silica particles is not known, but the explanation probably lies in the reduced bilayer rejection and the formation of different types of direct bonds or bridges.

Using concrete superplasticizers such as sodium salt 20 of a highly condensed naphthalene sulfonic acid / formaldehyde condensate, typically of which more than 70% consists of molecules containing 7 or more naphthalene cores, it is easy to obtain an extremely good dispersion of the ultrafine silica combined system, Portland cement and water, quilted enables the tight packing of the binder in a low-tension region.

Thus, the beneficial effect of superplastifiers in ultrafine silica / cement / water DSP systems is not due to the ability of superplastifiers to disperse ultrafine particles in water (other surfactants are even better for this purpose), but because is capable of providing a good dispersion of silica in the specific Portland cement / water environment.

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COMPOSITION MATERIALS STRUCTURE AND PROPERTIES

The present invention provides several novel methods and principles for establishing DSP materials, which are discussed in separate sections below. This section deals in particular with the establishment of ultra-strong cement-based DSP materials.

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

10 The reason is that the binder is the weak point in normal concrete and that fracture is preferentially obtained through the binder without passing the sand and rock particles.

In textbooks on concrete construction, this is clearly expressed by assuming, as a first approximation, that the strength alone is a function of the composition of the binder (expressed as the cement concentration of the cement-water suspension at the reciprocal value: "the water-cement ratio ") without including the quantity and quality of the sand and stones in the models.

In concrete, where the strength of the sand and stones is no longer high in relation to the strength of the binder, both the strength of the binder and the strength of the sand and stones are important for the strength of the composite material.

This is known in connection with traditional lightweight aggregate concrete, in which the rock material consists of light, porous, relatively weak material.

In this case, the strength of the bricks is equally important for the mortar strength in the mathematical expression of the concrete strength: η 1 -n σ - σ «x σ m where σ denotes the compressive strength, aa denotes the compressive strength of the bricks, am denotes the mortar compressive strength, n denotes the volume concentration of the stones and 1-n denotes the volume concentration of the mortar. In such ma 18

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terial extends the fracture extensively through the weak rock particles.

In the development of the new, very strong cement-based DSP binding agents, as described in International Patent Application no.

5 PCT / DK79 / 00047, concrete and mortar with a new strength have been obtained. Thus, International Patent Application no.

PCT / DK79 / 00047 water-cured wet cylindrical specimens with a diameter of 10 cm and a height of 20 cm which exhibit a compressive strength of 146.2 MPa for a concrete after 169 days of storage at 20 ° C and 179 MPa for a 10 mortar hardened by approx. 60 ° C for 4 days. Both the concrete and the mortar are made from light-flowing masses cast under light mechanical vibration. Ordinary quartz sand and, in the case of concrete, granite stones are used. These strengths were compared with the highest strengths described in the relevant technical literature: 15 120.6 MPa measured on sample cylinders of the same dimensions as above and consisting of concrete with a water / cement ratio of 0.25, a cement content * 5 of 512 kg / m and a content of "Mighty®" (a concrete superplasticizer described below) 150 of 2.75% of a 0.42% rs solution calculated on the weight of cement. The samples had been stored for one year prior to 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, under the Canada Center for Mineral and Energy Technology, Department of Energy, Mines 25 and Resources, Ottawa, Canada and American Concrete Institute,

Detroit, U.S.A.'s excellent).

A study of fracture surfaces in connection with the strength measurements described in International Patent Application No. PCT / DK79 / 00047 has shown that the sand and stone materials used were not strong in comparison with the binder, as would have been the case. in normal concrete, with the fracture largely passing through the sand and rock particles.

This showed the possibility of making even stronger concrete by combining the use of DSP binder with the use of much stronger

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19 sand and stone material. This is a principle which has no significant effect in the case of normal concrete, as explained above.

The combination of DSP binder with very strong sand and rock materials is one of the main aspects of the present invention.

According to this aspect, concrete and mortar are prepared with the DSP binder using e.g. refractory bauxite and silicon carbide as sand and stone material, both of which are much stronger than ordinary concrete sand and stone, cf. Examples 1 and 4.

10 The concrete and mortar are made of lightweight fluxes and have extremely high strength (the compressive strength of cylindrical concrete specimens with a diameter of 10 cm and a height of 20 cm cured at 60 ° C for 4 days is 217 MPa).

This is more than 50% higher than the strength of the very strong concrete 15 with traditional sand and stone bound together with the new strong cement binder (146.2 MPa, cf. international patent application no.

PCT / DK79 / 00047) and more than 80% higher than the highest compressive strength obtained, according to the applicants' knowledge, with concrete made with traditional soft pulp casting and curing technique using 20 traditional superplasticizing cement binder (120.6 MPa, cf. Hattori, loc .cit.).

The new high quality material of the present invention also exhibits an extremely high stiffness (dynamic elastic modulus of 109,000 MPa), which is approx. 60% higher than for high quality concrete with 25 DSP binder and quartz sand and granite stone, cf. Example 1 in International Patent Application No. PCT / DK79 / 00047.

The sand and refractory bauxite mortar is even stronger and stiffer than the concrete (the compressive strength of cylindrical specimens with a diameter of 10 cm and a height of 20 cm cured at 80 ° C for 4 days was 248 MPa and the 30 dynamic modulus of elasticity was 119,000 MPa, cf. Example 4). The compressive strength is 38% higher than the strength of the strongest mortar made with the DSP binder and quartz sand (179 MPa, cf. Example 9 in

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20 International Patent Application No. PCT / DK79 / 00047) and more than twice the strength of the above-mentioned strong concrete (120 MPa) described by Hattori. Even stronger cement-based DSP materials of the present invention have been produced with the strong sand and 5 rock materials, cf. Example 5, where the strength was 268.3 MPa.

Thus, the concrete material of the present invention is of novel quality obtained using extremely strong sand and stone material together with the extremely strong DSP binder, thereby utilizing the strength of the sand and stone materials better compared to ordinary concrete, and 2) The strength of the DSP binder is much better utilized than in concrete with the usual sand and stone material.

Together with the advantages of light manufacturing associated with the DSP binder, the incorporation of the particularly strong sand and stone materials opens up a wide range of new and improved products.

Another very interesting aspect of the ultra-strong cement-based DSP materials is the ratio of strength σ to density #, which is the key parameter in the construction of large structures such as towers, bridges, etc., where the maximum size is proportional to this ratio. The strength / density ratio of cement-based DSP materials, especially DSP materials containing strong sand and stone, is far higher than the strength / density ratio of ordinary concrete 25 or high quality concrete and even higher than the strength / density ratio of structural steel, cf. in the section "GREAT CONSTRUCTIONS" below.

The aspect of the present invention, which relates to ultra-strong cement-based DSP materials, can be defined as shaped articles 30 containing a coherent matrix, the matrix comprising 21

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A) homogeneously arranged inorganic solid SiC4-rich particles of a size of from ca. 50 Å to approx. 0.5 μια, or a coherent structure formed from such homogeneously arranged particles, and 5 B) tightly packed solid particles of the order of 0.5-100 μια and at least one order of magnitude larger than the respective particles mentioned under A), or a coherent structure formed from such tightly packed particles, at least 20% by weight of the particles being Portland cement-10 particles, the particles A or the coherent structure formed therefrom being homogeneously distributed in the space between the particles B, wherein the particles A are present in an amount that is 5-50% by volume of the total volume of the particles A + B, and the dense gasket is essentially a gasket similar to that obtainable by gentle mechanical action of a system of geometrically similarly shaped large particles in which locking surface forces have no significant effect, a concrete superplasticizer, since the amount of superplasticizer solid is in the range of 1-4%, based on the total weight of the particles A + B, which further comprises formed, embedded in the matrix 25 C) compacted solid particles of a material having a strength exceeding the strength of ordinary sand and stone used for ordinary concrete, typically a strength corresponding to at least one of the following criteria: 1 a piston pressure greater than 30 MPa at a packing rate of 30 0.70, above 50 MPa at a packing rate of 0.75 and over 90 22

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MPa at a packing rate of 0.80, determined by the method described herein (on particles of a material having a size ratio of the largest to the smallest particle substantially not exceeding 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 is greater than 4 mm) and 200 MPa (in the case that substantially all particles are less than 4 mm) ), determined by the method described herein, 3) a Moh hardness (for the mineral made up of particles) exceeding 7, and 4) a Knoop indentor hardness (for the mineral made up of particles 15), exceeding 800, these particles having a size of 100 / tube-0.1 m, and optionally D) additional bodies having at least one dimension at least one order of magnitude larger than the particles A, 20 having formed the article manufacture t using a weight ratio of water to particles A + B of 0.12-0.30.

According to the above aspect of the invention, sand and stone materials which are stronger than the sand and stone materials used in ordinary concrete are used. Concrete sand and stone typically consist of common stone materials such as granite, gneiss, sandstone, flint and limestone containing such minerals as quartz, feldspar, mica, calcium carbonate, silicic acid etc.

A further aspect of the invention relates to a composite material for producing a shaped article which contains,

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A) inorganic SiC4-rich particles of about size 50 Å to approx. (B) solid particles of the order of 0.5 to 100 μπι, which particles are at least one order of magnitude larger than the 5 corresponding particles mentioned under A), with at least 20% by weight of the particles being Portland cement particles; and wherein the amount of particles A is 5-50% by volume of the total volume of particles A + B, C) compact shaped solid particles of a material having a strength exceeding the strength of ordinary sand and rock used for ordinary concrete typically a strength corresponding to at least one of the following criteria: 1) a piston pressure greater than 30 MPa at a packing rate of 0.70, above 50 MPa at a packing rate of 0.75, and more than 90 15 MPa at a packing rate of 0.80 determined by the method described herein (on particles of a material having a size ratio of the largest to the smallest particle which does not substantially exceed 4), 2) a compressive strength of a composite material wherein the particles e. r is 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 the case of substantially all particles being less than 4 mm) determined by the 3) a Moh hardness (for the mineral comprising the particles) exceeding 7, and 4) a Knoop indentor hardness (for the mineral comprising the particles) exceeding 800, these particles have a size of 100 μπι-0.1 m, 24

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and a concrete superplasticizer, the amount of super-plasticizer drying being in the range of 1-4%, based on the total weight of particles A + B, the amount of particles B substantially corresponding to its tight packing in the homogeneously packed composite material particles A in the space between particles B, and the amount of concrete superplasticizer is sufficient to impart a liquid to plastic consistency to the composite material in a low stress range of less than 5 kg / cm 2, preferably less than 100 g / cm 2 a water-10 amount is added which is substantially equal to the amount needed to fill the voids between particles A and B, this amount corresponding to a weight ratio of water to particles A + B of 0.12-0 , 30, and optionally D) additional bodies having at least one dimension 15 at least one order of magnitude larger than particles A.

Different kinds of comparison experiments can be used to determine that certain sand and rock materials are stronger than ordinary concrete sand and stone, e.g.

1) measurement of hardness 20 2) determination of the crushing strength of a single particle 3) hardness of the minerals of which the sand and rock materials are composed 4) determination of the resistance to powder compression 5) wear tests 25) grinding tests 7) measurement of strength of a composite material containing the particles.

It is difficult to state unambiguous relationships between such strength and hardness results for sand and stone and the ability of this sand and stone to impart strength to the concrete or mortar.

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It is generally assumed that sand and rock with higher hardness, abrasion resistance, strength in composite structure etc., provide a higher concrete strength, provided that 1) there is identical particle geometry (particle shape, particle size, volume and degree of packing) and 2) the concrete systems are systems where the fracture passes to some extent through the sand and rock particles. (If this latter condition is not met, as mentioned in the preamble of the specification, it is due to the fact that the sand and rock material is in all cases much stronger than the matrix, and that a further increase in the strength of the sand and rock material has no influence. on the quarry, the quarry then in all cases passing through the matrix and avoiding the sand and stone particles.) 15 In Examples 1, 3, 4 and 5, sand and stone materials with substantially higher strength and hardness than ordinary concrete are used:

Refractory bauxite containing 85% Al 2 O 3 (corundum) and silicon carbide was used. Both materials have significantly higher hardness than the minerals in the usual sand and rock. Thus, both corundum and 20 silicon carbide are stated to have a hardness of 9 according to Moh's hardness scale, and the Knoop indentor hardness is stated to be 1635 -1680 for alumina (corundum) and 2130 - 2140 for silicon carbide, while quartz, which is one of the hardest. minerals in the usual concrete sandstone, have a Moh hardness of 7 and a Knoop indentor hardness of 710 - 790 25 (George S. Brady and Henry R. Clauser, Materials Handbook, 11th edition,

McGraw - Hill Book Company).

The high strength of sand and rock fractions of these materials compared to usual concrete sand and stones has been demonstrated in powder compression experiments (Example 3) and in mortar and concrete experiments with silica cement binders using the materials as sand and stone (Example 1, 4 and 5).

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Of course, many materials other than the above two materials can be used as strong sand and stone materials. Typically, materials having a Moh hardness greater than 7, e.g. topaz, law-sonite, diamond, corundum, phenacite, spinel, beryl, chrysoberyl, tourmaline, andalusite, staurolite, zircon, boron carbide and tungsten carbide.

The hardness criterion can, of course, also be indicated by Knoop indentor hardness, where minerals with values above the value for quartz (710-790) must be considered as strong materials compared to the minerals that form the usual concrete sand and rock. For the determination of the strength 10 of sand and rock, the technique described in Examples 1, 4 and 5, which comprises embedding the relevant sand and stone material in a specific cement / silica matrix manufactured and tested, can be used. in a specific way:

Concrete (the size of the largest particles is more than 4 mm): 15 Concrete made from the usual concrete sand and stone materials (granite and quartz sand) and silica / cement matrix which is essentially identical to that used in Example 1, has compressive strengths of approx. 120-160 MPa (cf. International Patent Application No. PCT / DK79 / 00047). Therefore, it seems reasonable to characterize rock and sand materials, which increase the concrete's compressive strength to 170 MPa, as strong in comparison with the usual concrete sand and stone. With sand and stone materials of refractory bauxite, however, cf. Example 1 of the present application, obtained strengths of 217.5 MPa, for which reason 25 values greater than 200 MPa can be considered as a realistic and desirable target for a preferred material.

Mortar (particle size not exceeding 4 mm):

Analogous experience has been gained with cement / silica / mortar, where the materials with substantially identical cement / silica matrix gave compressive strengths of 160 - 179 MPa for quartz sand mortar (cf. example 9 in international patent application no.

PCT / DK79 / 00047) and 248 and 268 MPa, respectively, for mortar with refractory bauxite sand (Example 4 and Example 5 in frf 27, respectively)

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this application). It seems reasonable to designate sand that increases mortar strength to over 200 MPa, as strongly compared to the strength of normal sand, and it also seems reasonable to specify strengths above 220 MPa as a target both desirable and achievable by the preferred materials.

For the assessment of aggregates with a particle size greater than 4 mm, the concrete technique of Example 1 is used. For the evaluation of sand with a particle size of less than 4 mm, the mortar technique is used, cf. Example 9 of International Patent Application No. PCT / DK79 / 00047 and 10 Examples 4 and 5 of the present application (composition as for bauxite mortar), the same mixtures having to incorporate the same volume of sand and stone, not the same amount of sand and stone. The preparation, curing and testing are carried out as in the examples mentioned.

The above test methods and the particular manner in which certain of the experiments are carried out form the basis of the definition of usable and preferred particles C in the claims.

The additional bodies D, having at least one dimension that is at least one order of magnitude larger than the particles A, may in principle be 20 bodies of a solid (as described in more detail below), a gas (such as in gas concrete). , or a liquid. The bodies may be compact-shaped bodies (such as sand, stone, gas bubbles or liquid bubbles), plate-shaped (such as mica particles) or elongated (such as fibers or reinforcing bars or ropes). Due to the possibility of shaping the articles in question in a "gentle" manner in a low voltage region, these bodies, contrary to what is known in all known compression methods which could possibly result in tight packing, ultrafine particle systems, essentially retaining their geometric identity during molding. In this context, maintaining a geometric identity must indicate that the bodies in question are not subjected to any significant crushing or drastic deformation. A typical example is a solid body in the form of a hollow particle or fiber which would be crushed or drastically deformed by powder compression or other treatment in a high voltage region, but as in the region of much lower voltage.

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28 in which the articles of the invention can be formed are capable of avoiding such degradation.

Examples of additional bodies D which may advantageously be incorporated into shaped articles comprising the DSP matrix are metal bars, including steel bars, fibers including metal fibers such as steel fibers, plastic fibers, glass fibers, Kevlar fibers, asbestos fibers, cellulose fibers, mineral fibers, high temperature fibers and "whiskers" including inorganic non-metallic whiskers such as graphite whiskers and Al2Ο3 whiskers and metallic whiskers such as iron whiskers, heavy components such as 10 barite or lead or lead-containing mineral particles, and hydrogen-rich components such as hollow water-filled particles. When the articles of the invention contain additional bodies D, it may be attractive to obtain optimum strength and stiffness or for other purposes to obtain tight packing of the additional bodies. The easily deformable (easily flowable) DSP matrix allows for a substantially closer arrangement of additional bodies than was possible in the prior art.

Especially the incorporation of fibers is of great interest because of the unique ability of the DSP matrix to anchor fibers. In this connection, it should be mentioned that the much denser structure of the shaped articles containing the DSP matrix will lead to practically an insulation of fibers which would otherwise be subject to chemical attack from the constituents of the matrix or from the surroundings. The fibers used in the articles of the invention may be of any configuration such as single-stranded or continuous fibers or yarns or ropes, or yarns or staple fibers, or fiber nets or webs. The particular fiber type and configuration will depend on the particular field of application, the general principle being that the larger the dimensions of the shaped article, the longer and coarser the preferred fibers.

The improvement of the fixation of fine fibers makes it possible to fabricate greatly improved fiber composite materials based on the fact that a greater amount of over-cut fibers are mixed in the material than in similar materials based on conventional matrices. In order to ensure that the fiber 35 works well in the known matrices, it is necessary that they

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bored fibers have a certain (high) length-to-diameter ratio, the so-called aspect ratio. In normal matrices, however, it is difficult to mix and apply fibers with large aspect ratios - in other words, the smaller the aspect ratio, the easier it is to incorporate the fibers and arrange them in a suitable manner in the molded matrix, and the higher the fiber volume can be. that is incorporated. Thus, e.g. chopped polypropylene fibers with cross dimensions of approx. 30 μτα is usually a length of 12 - 25 mm (aspect ratio over 500) when used as reinforcement in conventional cement matrices. A much better utilization of the same type of fibers is achieved in the DSP matrix of the invention, as described in Example 2 of International Patent Application No. PCT / DK79 / 00047. In Example 2 of International Patent Application No. PCT / DK79 / 00047, a very favorable fixation and resultant strength properties were obtained, although the fiber length was only 6 mm. With the DSP-15 matrix, it seems possible to reduce the length of the chopped fiber and, thus, the aspect ratio, by a factor of 10 or more (compared to the chopped fiber with ideal or reasonable aspect ratio for use in normal matrices), and therefore, utilizing this reduced aspect ratio to incorporate a greater amount of 20 fibers into the composite material and / or ensure a better fiber arrangement in the molded matrix.

Among the most important objects containing the DSP matrix are those in which the particles B comprise at least 50% by weight of Portland cement particles, especially those in which the particles B consist essentially of Portland cement particles. These shaped articles will typically contain silica dust particles in a volume of about 5 - 50% by volume, especially 10 - 30% by volume, of the total volume of particles A and B, and will typically contain sand and stones as additional bodies, so that they are of extremely high quality mortar or concrete in mechanical strength, frost resistance, etc., and / or fibers, in particular metal fibers including steel fibers, mineral fibers, glass fibers, asbestos fibers, high temperature fibers, carbon fibers and organic fibers, including plastic fibers, to provide fiber reinforced products with a unique anchoring of the fibers as is -35 written above. Especially with regard to fibers which are subject to chemical degradation, e.g. glass fibers which are subject to degradation under highly alkaline conditions are an important advantage of the

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According to the present invention, these fibers are much better protected against environmental influences both during the curing and in the final cured material, due to partial dissolution of the silica dust with resultant partial neutralization of the alkaline environment, as well as the micro-dense " jacket "around the fibers constituted by the ultrafine particles and the coherent structure formed therefrom, which contributes very substantially to static conditions in the glass fiber environment, thereby substantially avoiding any migration of alkaline material to the fiber in the finished army. that matrix.

When the shaped articles of the invention are of large dimensions, they are preferably reinforced with reinforcing steel such as beams or rods or steel wire or fibers. The reinforcements in prestressed constructions containing the DSP matrix are particularly valuable. Due to the 15 delicate conditions under which the articles can be formed, the reinforcing bodies can retain their geometric identity during the molding process. A combination which exhibits the matrix structure and reinforcing steel described above, which has retained its geometrical identity during the forming process, has hardly been obtainable in any known system.

With the greatly increased strength of the binder matrix and the greatly improved fixation of fibers and rods in the matrix, it is possible to make new classes of articles and materials based on reinforced and fiber-reinforced cement: 1) Fragile materials with very high tensile strength obtained at to incorporate high quality fine fibers or whiskers (fibers or high tensile strength and high elasticity modulus, eg glass fibers, carbon fibers, asbestos, AI2O3 whiskers) in medium to large volume concentration in the binder matrix.

30 2) Semi-tough materials with high tensile strength and relatively high tensile strength, produced by incorporating relatively fine, high quality fibers with high tensile strength and relatively low elastic modulus in medium to high volume concentration in

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31 the binder matrix (eg high strength polypropylene fibers and Kevlar fibers).

3) High quality prestressed reinforced articles, the quality of which is first and foremost achieved by incorporating a much higher volume of high quality steel rods or wires than is usually used (the volume of reinforcement that can be used is direct proportional to the compressive strength of the matrix) in a matrix of the novel type according to the invention. In usually prestressed concrete, the volume of prestressed steel is as low as 1-2%, calculated on the concrete.

The volume of steel is limited by the compressive strength of the concrete. An increase in compressive strength by a factor of 4 could e.g. is fully utilized to bias bodies to secure a 4 times higher bending strength or to reduce body height by half. Such bodies would require a non-unrealistically high bias steel volume (4 - 8%). It would also be possible to use the improved matrix material in prestressed articles with much smaller cross-section than in traditional prestressed concrete objects, with the corresponding application of finer prestressing reinforcement (thin threads). Despite the larger specific surface, the wires are well protected in the new dense matrix material, which effectively shields the wires from any environmental influences.

4) Objects of reinforced, non-prestressed concrete, where the improved quality of the matrix material is first and foremost utilized by incorporating steel rods or wires of much higher tensile strength than conventional iron concrete. The use of an increased amount of a conventional reinforcement to utilize the increased quality of the matrix would in many cases require an unrealistically large amount of reinforcement. High-quality reinforcing bars used in ordinary concrete have a surface designed to secure the anchorage of the reinforcing bars in the concrete (deformed bars; cam steel; tentor steel, etc.).

Such rods have a strength of not more than 900 MPa and therefore they do not have the same high strength as the best cold drawn smooth

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32 rods and threads used e.g. in prestressed concrete, which typically has a strength of 1800-2200 MPa. On the other hand, smooth threads and rods do not ensure adequate fixation in ordinary concrete. The greatly improved fixation achieved in the DSP matrix allows for the advantageous use of the very high strength smooth steel wires and rods as non-prestressed reinforcement. Due to the high stresses resulting from full utilization of the high-quality steel and the corresponding cracks that will appear in the concrete (as in the usual reinforced concrete), it is advisable especially to utilize the above-mentioned technique in thin bodies in combination with fine reinforcement to secure a crack pattern with many finer spaced thin cracks.

Of course, the mentioned reinforcement options can be combined in many ways, e.g. by fabricating a thin coating of semi-skirted reinforced material on a large bearing member or by using high quality steel wire as secondary reinforcement (predominantly located perpendicular to the main reinforcement) in large prestressed bodies.

When strongly sand and rock (bodies C) are embedded in the matrix in accordance with the aspect described above of the present invention, the resulting high quality materials can be characterized by having a compressive strength greater than 150 MPa. preferably more than 180 MPa, measured on a test body having a diameter of 10 cm and a height of 20 25 cm, and the largest of the compact shaped bodies being greater than 4 mm and more than 180 MPa, measured on a test body , with a diameter of 3 cm and a height of 6 cm, when the largest of the compact-shaped bodies is at most 4 mm, 30 with the proviso that the shaped article has at least one dimension which is at least one meter and a cross-section of at least 0.1 m 2, and / or a complex form which does not allow its preparation by powder compression.

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CHARACTERISTICS OF THE LIQUID STRUCTURE; HORIZONTAL TION

By introducing ultrafine particles into the cavities between densely packed particles, e.g. silica particles with a specific surface area of 250,000 cm 2 / g, in the spaces between cement particles having a diameter of 5 5 μια, a structure is obtained which exhibits improved resistance to internal mass transport in the form of fluid transport (gas or liquid) between the particles and mass diffusion in the pore fluid.

The extrusion of liquid from saturated particle systems depends on the compression of the particle skeleton - which typically depends on whether slippage between the particles is possible - and on the flow of liquid through the channels between the particles.

In forming cement-silica-water suspensions, internal fluid transport in the fresh material is essential. The resistance to viscous flow of fluid between particles 15 in systems of particles of geometric uniformity varies inversely with the square of the particle diameter.

This means that the time of a given liquid transport under a pressure gradient in two geometrically similar particle-liquid systems with a particle size ratio of 1:50 is 2500 times longer in the fine-grained system than in a system of particles 50 times so big.

A similar effect is obtained by filling the pore volume between large particles with ultrafine particles, since it is the cross-sectional dimensions of the resulting channels between the particles that are crucial for the resistance to flow.

The effect of particle size on water retention is further illustrated in FIG. 6, 7 and 8. These conditions are well known and it is also known to reduce the internal fluid transport in cement / water systems by introducing so-called "thickening agents" into the water in the form of ultrafine particles or polymers such as Methocell.

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However, due to the dominant effect of locking surface forces, it will normally not be possible to combine the utilization of 1) very dense cement packing and 2) ultrafine particles in a light liquid aqueous suspension.

However, with an extremely high dosage of a superplasticizer, this is possible. Thus, light-flowing cement paste, mortar and concrete can be prepared with tightly packed cement particles and containing 10 - 30% by volume of silica dust, calculated on cement + silica dust, with weight ratio water / cement plus silica dust of 0.15 - 0.20.

This leads to many advantages over the known methods: 1. Preparation of superfluidized cement product without bleeding

In the known preparation of high quality concrete and mortar, where relatively high doses of superplasticizer are used, a low flow mass with a low water / cement ratio (eg 0.25) is obtained.

15 The mass is poured into molds where it is compressed under the influence of gravity and possibly also mechanical vibration. During this process, however, the heavier cement, sand and rock particles will tend to settle into an even denser gasket while water migrates upward, the so-called bleeding, cf. FIG. 7th

In such known systems with very effective cement dispersion obtained by the use of relatively high doses of superplasticizer, pronounced bleeding is usually observed despite the low water / cement ratio - especially if the process is accompanied by vibration. This phenomenon can e.g. be critical in the casting of concrete roads with super-plasticized concrete, as the bleeding leads to a surface water with a high water content and can therefore lead to a road surface which is of lower quality than the intended wear layer. Internal fluid separation is also critical when casting reinforced concrete with superplasticizer. The liquid secretion can lead to bleeding on the underside of the reinforcement, reducing the fixation of the reinforcement and reducing the protection against chemical attacks.

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When, in accordance with the principles of the present invention, ultrafine particles, e.g. 5-15% silica dust of the above particle size, between the densely packed cement particles and using a high dosage of superplasticizer, results in a 5 drastic delay of the bleeding process, theoretically corresponding to 100 - 1000 times slower water movement (cf. Fig. 8). In practice, this means that bleeding is avoided, given that the chemical structure formation process usually begins and develops much faster.

In other words, by utilizing the above principle of the invention, which combines a high dosage of superplasticizer with silica dust, it becomes possible in practice to produce high quality superfluidized concrete, mortar and cement paste without bleeding. This is of particular interest in connection with prestressed structures, where the above principles can be applied to the manufacture of high quality non-bleeding, high-quality injection mortar (filling mortar) which provides extremely good protection of the prestressed reinforcement and ensures extremely good mechanical fixation, cf. . the more detailed description of this aspect in the following.

2. Manufacture of high quality cement products in an area of low voltage and without liquid transport to the surroundings

In the manufacture of certain cement products, e.g. Asbestos cement sheets, in the prior art, either a slip casting technique 25 (where excess liquid is pressed from an aqueous slurry through filters, cf. the Magnani process where the extrusion is established via a vacuum system) or a high pressure extrusion of moist powder (where a traditional thickening agent (Methocell) has been added to avoid the otherwise hardly avoidable internal fluid transport at the mouth and the resulting blockage of the system due to mutual particle locking).

According to one aspect of the present invention, it is possible to produce such materials in a low voltage region by simple rolling processes or extrusion without fluid exchange.

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36 with the environment when a high amount of superplasticizer is incorporated into the pulp together with ultrafine particles.

While it would seem possible to use similar rolling or extrusion processes with cement materials incorporating 5 high amounts of superplasticizers, but without the concomitant use of ultrafine particles peculiar to this aspect of the present invention, such materials would - although could be easily liquefied with a low water / powder ratio (but not quite as low as with ultra-fine, well-dispersed particles) - due to the large size of the cement particles have a pronounced tendency for local water extinction in the stress zones, such as at the rollers or at the extruder outlet, thereof following the blocking of the particles. This has been observed in practice by experiments with a laboratory extruder with superplasticized fine-grained cement and with superplastified ordinary cement + an addition of fine filler material which was finer than the cement but substantially coarser than the above-mentioned ultrafine silica dust. In both cases, the material had a sandy behavior and could not be extruded due to blocking.

With an ultra-fine silica powder incorporated into the superplasticized cement system in accordance with the principles of the present invention, such extrusion of water is delayed by a factor of the order of 100-1000 (calculated theoretically). The cement silica material containing a high amount of superplasticizer appears tough viscous and cohesive during rolling, whereas similar superplasticized products without the ultrafine silica powder typically appear as friction materials with a tendency for local water pressing with resultant particle blockage during rolling.

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3. Manufacture of flowing materials with high internal consistency

Light-flowing superplasticized cement materials containing ultra-fine silica particles are an aspect of the DSP principle and have a much better internal consistency than corresponding superplasticized light-flowing cement materials without ultra-fine silica particles. It is believed that the reason for this is that local fluid transport, which would contribute to separation, is drastically reduced in the materials with the ultrafine silica particles.

(This is shown in Fig. 10, which illustrates a demonstration of the inner 10 coherence of a liquid to plastic mortar. Exposure to flowing water (4 liters per minute) for typically 5-30 minutes will not lead to any visible washout of material from the mortar.)

In this way, many benefits are obtained. Eg. a significant improvement has been achieved in the existing possibilities of making 15 underwater concrete simply by pouring the fresh concrete into the water.

This technique is known per se and is especially developed with super-plasticizing additives (without ultra-fine powder). However, with ultra-fine, well-dispersed silica powder in accordance with the principles of the present invention, the process is much more attractive and has similarly expanded potential applications.

Resistance to internal fluid transport increases with the density of the packing of the ultrafine particles in the spaces between the coarse particles. Thus, it is expected that fluidized powder materials consisting of well-dispersed Portland cement (s - 4000 cm 2 / g) and si-25 lica dust (s - 250,000 cnr / g) will exhibit significantly improved internal consistency, better resistance to internal fluid flow and bleeding. and better machinability in rolling and extrusion with 20 - 40 volume percent silica dust than with 5-10 volume percent silica dust. However, the experience gained so far indicates that even very small amounts of ultrafine silica dust (typically 1-5%) are incorporated between densely packed particles B, especially densely packed Portland cement.

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structures, can have a pronounced enhancing effect compared to similar materials without silica dust.

PRODUCTION METHODS.

Articles containing the DSP matrix may be formed in a low voltage region from a composite material containing A) inorganic SiO2-rich particles of about size. 50 Å to approx. (B) solid particles of the order of 0.5-100 μπι, which particles are at least one order of magnitude larger than the 10 corresponding particles mentioned under A), with at least 20% by weight of the particles being Portland cement particles; and wherein the amount of particles A is 5-50% by volume of the total volume of particles A + B, C) compact shaped solid particles of a material having a strength greater than the strength of ordinary sand and rock used for ordinary concrete. typically a strength corresponding to at least one of the following criteria: 1) a piston pressure greater than 30 MPa at a packing rate of 0.70, above 50 MPa at a packing rate of 0.75, and more than 90 20 MPa at a packing rate of 0.80 determined by the method described herein (on particles of a material having a size ratio of the largest to the smallest particle which does not substantially exceed 4), 2) a compressive strength of a composite material wherein the particles e. r is 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 the case of substantially all particles being less than 4 mm) determined by the the method described herein, 39

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3) a Moh hardness (for the mineral made up of the particles) exceeding 7, and 4) a Knoop indentor hardness (for the mineral made up of the particles) exceeding 800.5, these particles having a size of 100 μιη-0.1 m, water in a weight ratio of water to particles A + B of 0.12-0.30, and a concrete superplasticizer, the amount of super-plasticizer drying being in the range of 1-4%, calculated on 10 total weight of particles A + B, wherein the amount of particles B substantially corresponds to tight packing thereof in the composite material with homogeneously packed particles A in the space between particles B, the amount of water substantially corresponds to the amount needed for filling of the space between particles A and B, and the amount of concrete superplasticizer is sufficient to impart a liquid to plastic consistency to the composite material in a low stress range of less than 5 kg / cm 2, preferably less than 100 g / cm 2 and optionally 20 D) additional bodies having at least one dimension at least one order of magnitude larger than particles A.

It should be noted that although the amount of superplasticizer in claim 25 is defined, inter alia, by the conditions to be fulfilled so that the amount is sufficient to disperse the 25 particles in a low voltage region (which otherwise indicates the use of an extremely high amount of superplasticizer), this does not mean that the composite material is necessarily used in a low voltage region; it can also be used in a higher voltage area. Objects with tightly packed superfine particles are obtained from a composite material of the type specified above, wherein 40

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the particles A are present in a volume which substantially corresponds to tight packing to fill the space between the particles B when tightly packed.

The superplasticizer is present in an amount sufficient to allow tight packing of the particles A) in a low voltage range of less than 5 kg / cm 2, preferably less than 100 g / cm 2, and the ideal amount of superplasticizer is one which substantially corresponds to the amount which can completely absorb the surface of the particles A. FIG. 2 of International Patent Application No. PCT / DK79 / 00047 discloses ultrafine silica particles covered with a layer of a superplasticizer "Mighty®", the composition of which is described below. Assuming that the super-plasticizer is absorbed in a uniform layer on the surface of the silica balls, the calculated thickness according to the applicants' own experiments was 25 - 41 Å, corresponding to a volume of 14 - 23% of the volume of the balls. It should be noted that an excess of the superplasticizer relative to the amount which will completely absorb the surface of the ultrafine particles will not be advantageous and will only help to take up too much space in the composite.

For the purposes of the present invention, any type of concrete superplasticizer may be used which will sufficiently disperse the system in a low voltage region. The type of concrete superplasticizer used in the experiments described in the Examples to obtain extremely valuable results in Portland cement-based systems is of the type comprising alkali or alkaline earth metal salts, especially a sodium or potassium salt, of a highly condensed naphthalene sulfonic acid / formaldehyde condensate, of which typically more than 70% by weight consists of molecules containing 7 or more naphthalene cores. A commercial product of this type is called "Mighty®" and is manufactured by Kao Soap Company, Ltd.,

Tokyo, Japan. In the Portland cement-based silica dust-containing composite materials of the invention, this type of concrete super-plasticizer is used in the high amount of 1-4% by weight, especially 2-4% by weight, based on the total weight of the Portland cement and the silica dust.

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Other types of concrete superplasticizers which can be used for the purposes of the present invention are set forth in Example 2 of the present application.

Portland cement-based composite materials of the type specified above will often contain additional fine particles of appropriate size and size along with the Portland cement particles, such as fine sand, fly ash and fine chalk, to obtain even denser binary structures formed. of the particles B in accordance with the principles stated above.

Both for its unique molding and machinability properties discussed above and illustrated in more detail in the Examples, and for their ability to gently retain and, in the finished molded state, effectively micro-lock or microencapsulating all incorporated additional bodies, the composite material exhibits outstanding beneficial properties not previously described or suggested for any material, and such new and highly useful composite materials therefore constitute important aspects of the present invention.

Interesting new composite materials of the invention are Portland 20 cement-based materials which as additional bodies contain bodies selected from the group consisting of fibers including metal fibers such as steel fibers, plastic fibers, glass fibers, Kevlar fibers, asbestos fibers, cellulose fibers, mineral fibers, high temperature fibers and whiskers, including non-metallic whiskers such as graphite whiskers AI2O3-25 whiskers and metallic whiskers such as iron whiskers, heavy components such as barite or lead or lead-containing mineral and hydrogen-rich components such as hollow water-filled particles.

Important composite materials of the invention are those materials in which the particles A are silica dust particles with a specific surface area 30 of approx. 50,000-2,000,000 crn ^ / g, especially approx. 250,000 cm 2 / g, and the particles B comprise at least 50% by weight of Portland cement. In these composite materials, the dispersant is a concrete superplasticizer in a high amount resulting in the above dispersing effect.

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In accordance with the principles discussed above, the composite material for the manufacture of the articles of the invention has a very low water-cement ratio and any other particles B plus silica dust, this ratio being 0.12-0.30 by weight, preferably preferably 0.12-0, -20 by weight and the silica dust may be present in a volume of approx. 5-50% by volume, especially 10-30% by volume, based on the total volume of particles A + B.

In accordance with a particular aspect of the present invention, the composite is packaged and shipped as a dry powder.

10, the addition of the liquid, typically water, being carried out at the point of use. IN

in this case, the superplasticizer is present in the dry state in the composite. 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, the final user merely adding the prescribed amount of liquid and performing the final mixing according to the regulation, e.g. in that way, is described in Example 11 of International Patent Application No. PCT / DK79 / 00047.

The invention also relates to a process for producing a shaped article, which involves combining 20 A) inorganic solid SiO2-rich particles with a size of from approx. 50 Å to approx. 0.5 µm and B) solid particles of the order of 0.5-100 μιη, which particles are at least one order of magnitude larger than the respective particles mentioned under A), with at least 20% by weight of the particles being Portland cement particles; and wherein the amount of particles A is 5-50% by volume of the total volume of particles A + B, water in a weight ratio of water to particles A + B of 0.12-0.30, 30 and a concrete superplasticizer, the amount of super - 43

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plasticizer solids are in the range of 1-4%, based on the total weight of particles A + B, where the amount of particles B corresponds substantially to tight packing thereof in the composite material with homogeneously packed particles A in the space between particles B, the amount of water substantially equal to the amount needed to fill the space between particles A and B, and the amount of concrete superplasticizer is sufficient to give the composite material a liquid to plastic consistency in a low stress range of less than 5 kg / cm 2; preferably less than 100 g / cm 2, and C) compact shaped solid particles of a material having a strength exceeding the strength of ordinary sand and stone used for ordinary concrete, typically a strength corresponding to at least one of the the following criteria: 1) a piston pressure exceeding 30 MPa at a packing degree of 0.70, above 50 MPa at a packing degree of 0.75 and over 90 MPa at a packing degree of 0.80; t by the method described herein (on particles of a material having a size ratio of the largest to the smallest particle substantially not exceeding 4), 2) a compressive strength of a composite material wherein the particles are enclosed in a specific matrix exceeding 170 MPa (in case a substantial amount of particles is greater than 4 mm) and 200 MPa (in case substantially all particles are less than 4 mm) as determined by the disclosure described herein 3) a Moh hardness (for the mineral made up of the particles) exceeding 7, and 4) a Knoop indentor hardness (for the mineral comprising the particles 30) exceeding 800, these particles having a size of 100 μπι-0.1 m,

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44 and optionally D) additional bodies having at least one dimension that is at least one order of magnitude larger than particles A and mechanically mixing particles A, water and concrete superplasticizer together with particles B and C and optionally additional particles D until a viscous to plastic mass is obtained and then, if necessary or desired, combines the resulting mass with particles and / or bodies of the above type (B, C, D) by mechanical means to obtain the desired distribution of the composition. 10, and finally, the resulting mass in the desired form casts in a low voltage region, optionally with incorporation, during casting, of particles C and / or additional bodies D.

It should be noted that the above low voltage range indicates the amount of superplasticizer to be used and does not necessarily mean that the process is in fact carried out in a low voltage range. However, the fact that the method can be carried out in a low voltage region constitutes one of the main advantages of the method, and preferred low voltage regions (preferably below 5 kg / cm 2 and more preferably below 100 g / cm 2) which used to form the mass are: gravitational forces acting on the mass, e.g. self-leveling of a molded soft mass, or inertia forces acting on the mass, e.g. by centrifugal casting, or contact forces, e.g. by compression, rolling or extrusion, or the simultaneous action of two or more of the above-mentioned types of forces, such as by combined vibration and compression. Also oscillating forces with a frequency between 0.1 and 10® Hz can be used to form the mass: these oscillating forces are of the type described above, such as forces derived from a mechanical or hydraulic vibrator, or such oscillating forces can be combined with non-oscillating forces such as by combined vibration and pressure compression.

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45

The superplasticizer is often added together with the water, so that an aqueous solution of the superplasticizer is added, but it is also within the scope of the invention to incorporate the water without it being in the form of a solution of the superplasticizer, combining the superplasticizer with the water. mixed deprocessen. It is characteristic that a blend that matches the above definition will have a very "dry" appearance during the blending step until it is converted to a viscous, plastic mass.

This "dryness" is due to the low liquid content.

Of course, the manufacturing technique for making the shaped articles according to the invention must be adapted specifically to the specific type of composite material and the specific type of shaped article concerned. However, there are some general guidelines: 1) The powders in the matrix (particles A and B) should preferably be dispersed as well as possible prior to mixing. If the dry state dispersion is insufficient, e.g. if the particles A are aggregated, some dispersing effect, e.g. grinding.

2) The mixing should ensure homogeneous distribution of the 20 solid particles A and B. This can be achieved by dry mixing or by wet mixing, where a premix of liquid and either particles A or particles B are mixed with the respective remaining particle type. This mixing step can be performed with or without additional bodies.

3) The incorporation of the water either to the dry mixed powder (Particles A + B) or to either Particles A or Particles B in the case of premixing a wet slurry as mentioned under 2) can be accomplished either by adding the powder to the water (preferably under strong mechanical agitation) or by adding water to the powder mass (preferably during heavy mechanical kneading). Which of these methods should be chosen will depend largely on experience. However, it is presently believed that in preparing a relatively light liquid mass from a well-dispersed powder, it is easiest to perform the mixing by adding the well-dispersed powder.

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to the stirred water to avoid the liquid meniscus between the particles that would occur in the opposite process where small amounts of water were added to the powder. On the other hand, when poorly dispersed ultrafine powder is added to the stirred water, the powder may not be sufficiently dispersed at the stresses introduced during the stirring, even with the addition of superplasticizer. In this case, it is preferable to incorporate the water into the powder during high shear kneading, as kneading in combination with superplasticizers can produce a significant dispersing effect. In the examples (which are predominantly based on Portland cement + silica dust) the method of adding water to the powder during kneading / mixing (with a fairly moderate shear stress of about 100 - 1000 g / cm 2) has been used. For the most liquid materials (mortar and concrete with water / (cement + silica) ratio of 15 0.18 - 0.20 wt%) it is believed that the opposite technique could have been used with equal success. However, for the more rigid mixtures (pastes for extrusion containing fibers and having a water / (cement + silica) ratio of 0.13 - 0.15% by weight), it is assumed that the opposite technique would not work at all; In these cases, a valuable portion of the mixing took place in the extruder, where a kneading occurred under relatively high shear (in the range of 1 kg / cm 2).

4) The superplasticizer is not necessarily introduced in the form of a solution in the water (it can also be added as a powder where it is mixed dry with the particles A and B). In some systems, it is preferred to moisten the surface of the particles with a portion of the water prior to the addition of the solution containing the superplasticizer, as recommended in the prior art with superplasticized Portland cement suspensions. This was also done in the cement silica experiments described in the Examples of International Patent Application No. PCT / DK79 / 00047, except in Example 11. It is noteworthy that the mixing time of the very dense wet mixture can be drastically extended compared to traditional blending. This was especially true for the relatively rigid mixtures 35 (extruded paste with water / (cement + silica dust) ratio of 0.13 - 0.15, cf. Example 2 in International Patent Application No. PCT / DK79 / 00047) and for the medium rigid mixtures (water / (cement + silica)

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47 licenses dust ratio of 0.15 - 0.16, cf. Examples 3 and 9 of International Patent Application No. PCT / DK79 / 00047, where a mixing time of approx. 15 and 5 minutes were needed to change the consistency from an almost dry appearance to an appearance such as a dough and 5 a liquid and viscous mass, respectively. For the concrete with a water / (cement + silica puff) ratio ^ of 0.18 there was also an extended mixing time, but not as pronounced as for the systems which had very low water / powder ratios. It is believed that the local transport of the molecules of super-plasticizer to and between the surfaces of the tightly packed solid particles is the time-consuming factor of the process (this transport is the more difficult, the smaller the water / powder ratio). The texture of the material is extremely sensitive to the amount of water.

Thus, very small amounts of additional water can change the consistency from stiff dough-like to slightly liquid. In a superplasticized cement-15 silica mixture, this change can be achieved by changing the water / (cement + silica dust) ratio from 0.14 to 0.18.

The introduction of the superplasticizer as a dry powder into the dry mixture prior to the addition of water seems to be an equally valuable way of preparing the molding composition of the invention. This is demonstrated in Example 11 of International Patent Application no.

PCT / DK79 / 00047, where this procedure was used and resulted in a mortar having substantially the same flowability and appearance as a mortar made from nearly the same components, but mixed as described above with the addition of the superplasticizer as a solution to the pre-wetted mixture (cf. Example 9, Blend # 1, in International Patent Application No. PCT / DK79 / 00047).

For any specific system, there is a level at which the system is saturated with superplasticizer and above which there is no beneficial effect by adding an additional 30 superplasticizer. This saturation point increases with decreasing water / (cement + silica dust) ratio. Above this level, the material is not sensitive to the amount of superplasticizer.

5) The incorporation of additional bodies C and optionally D can be performed at any stage of operation, e.g. during dry mixing 35 or after wet mixing, etc. The preferred technique to be used 48

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in the specific cases, depends on the nature of the additional bodies C and D and is a matter of experience. In the case of concrete and mortar, it is important to ensure a relatively tight seal of the added gravel to ensure that it is a relatively small space to be filled 5 with the dense binder matrix of the invention. When incorporating fine fibers, conventional techniques such as shaking, blending and kneading may be used. When continuous fibers or filaments are incorporated or pre-arranged fibers such as fiber nets or tissues, all in accordance with the prior art, a valuable fiber orientation or fiber arrangement can be obtained. In general, the same techniques can be used to incorporate additional bodies into the matrix of the invention as to known matrices, but since there are virtually no locking surface forces between the particles of the matrix of the invention, it will generally be easier to obtain an effective incorporation into the matrices of the invention.

6) The casting, including the compression, can be obtained in the above low voltage areas. The new type of material will be suitable for transport by pumping, since it is practically free from bleeding and since the mass has a viscous character. However, since the cast consists of a particulate material which exhibits practically no locking surface forces between the individual particles, vibration and especially high frequency vibration can greatly contribute to the casting, since the mutually oscillating displacement of neighboring particles will substantially facilitate the flow.

7) The solidification of the material according to the invention differs in two respects from the solidification of similar articles based on less tightly packed matrices:

First, the solidification will occur faster (early strength) as the structure is denser packed. Second, solidification may be affected by the relatively large amount of superplasticizer needed to obtain the specific structure. In the Portland cement-silica-Mighty® systems, high early strength has been achieved, but moderate deceleration of curing (4-8 hours) has been observed.

35 In the Portland cement-s ilica-Migh ty® sys terns concerned, it is shown, 49

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as could also be predicted on the basis of the expected calcium silicate hydrate structure formed, that extremely good quality can be achieved by curing at both approx. 20 ° C, 80 ° C, 200 ° C (autoclave), which means that the new matrix can be used for traditional low-temperature cure, heat cure and autoclave treatment. Heat curing (which in normal concrete leads to slightly less strength than low temperature curing) appears to be the most promising curing technique for the material of the invention.

In accordance with the foregoing, the volume of water incorporated by the process is preferably such that virtually no water escapes from the pulp during the forming process, which leads to several advantages over prior art processes where liquid, typically water, is present. is removed from the sludge during the molding process, typically by some type of filter pressing operation.

Although the method of the invention can be said to constitute completely new technology, it can also be considered a valuable modification of existing technology. In the manufacture of fiber cement products according to the Magnani process, e.g.

Forming (from a dilute cement / fiber / water slurry) by rolling while simultaneously removing water by suction. When ultrafine particles and the extremely high amounts of superplasticizers in accordance with the principles of the present invention are incorporated into the mass to be treated, these known technologies can be modified such that by extrusion or rolling at a forming pressure of up to 100 kg / cm For example, a (even denser) material is obtained from a viscous / plastic mass that already has the final low water content, so that no water or virtually no water is removed from the mass during the forming process, so no suction device is needed.

As mentioned above, additional bodies D (such as bodies C and to some extent bodies B) can be incorporated at various stages during the process, and these additional bodies D are of the various types described in detail in the previous text, of course with the one -35th limitation to certain types of additional bodies such as reinforcement 50

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bars or strands in prestressed concrete can only be incorporated during the casting step and not in any previous step.

Uniquely improved possibilities for submerged structures, especially underwater structures, are that a cement paste, mortar or concrete of the present invention in the form of a cohesive mass is poured into a liquid, typically in the sea water, a harbor or a lake, and the mass displaces part of the fluid and arranges itself as a coherent mass.

Other options for utilizing the extraordinary moldability properties of the viscous to plastic mass are to form objects by spraying, painting, or brushing with the intention of forming layers on other objects or forming an object layer by layer by injection or simple manual applying a layer of the pulp to a surface and adapting the pulp to the surface shape. Centrifugal casting technique is another attractive molding method useful in the process of the invention. In the same manner as described in International Patent Application No. PCT / DK79 / 00047, the articles of the invention can be further subjected to impregnation to further increase their strength and to improve their properties. The 20 preferred materials and methods for this impregnation are the same as in International Patent Application No. PCT / DK79 / 00047.

When the particles A are to be tightly packed in the materials of the invention, they are preferably in a size of from 200 Å to approx. 0.5 pm.

The particles A used in the examples are S1O2 particles formed from the vapor phase (in connection with the production of silicon metal in electric furnaces), but other ultrafine SiO2 containing particles can be used, especially those which is mentioned in International Patent Application No. PCT / DK79 / 00047. However, in the context of the present invention, too, the particles formed by growth from a vapor phase are preferred.

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51

Casting up against or between surfaces

A new use of concrete, mortar and similar materials is made possible with the extremely strong, room temperature moldable materials according to the invention and according to international patent application no.

5 PCT / DK79 / 00047, namely the casting of articles with an outer shell and with an inner part which is filled, in whole or in part, with the strong materials according to the invention and according to international patent application No. PCT / DK79 / 00047 (concrete, mortar, paste etc. ., reinforced or unarmed).

This allows the desired specific surface properties of the articles (chemical, optical, thermal, mechanical, etc.) to be combined with good mass properties (especially high mechanical strength and stiffness) and a simple manufacturing technique (separate manufacture of a shell with subsequent introduction of liquid concrete, mortar or paste). This is a particular aspect of the invention.

There are a number of advantages and potential benefits associated with the separate manufacture of hollow shells which are filled in whole or in part with the material of the invention and according to International Patent Application No. PCT / DK79 / 00047: 20 1) The manufacture of the surfaces (shells) of the articles can be occur independently of the manufacture of the inner supporting reinforced core, ie. under ambient conditions (in terms of temperature, pressure, external facilities, etc.), which are not limited by the requirements of the inner core (extrusion of plastic, manufacture of shells of glass or ceramics, etc.).

2. Very large and thin-walled bodies with monolithic reinforced core can be manufactured. It is e.g. it is possible to produce long stretches of pipes with monolithic strong reinforced core in the pipe walls (for example, in connection with pipelines 30 on the seabed, where hollow walls of plastic or similar places are given in desired places, the space is filled with stones and reinforcement, after which the pipes are filled with paste or mortar according to 52

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International Patent Application No. PCT / DK79 / 00047 or according to the present invention by injection).

Other bodies which can be manufactured in this way are ship hulls, large building sections, tunnel linings and the like.

5 3. The molding work is simpler than in structures where the reinforced concrete or mortar is first manufactured in a special form and then surface materials are applied. According to the principles of that aspect of the invention, the surface coating acts as formwork.

10 STRUCTURAL EDUCATION

Curing Contraction of Portland Cement-Based DSP Matrices

When solidifying the cement-based DSP material, a volume contraction occurs, as is the case with conventional cement paste. The volume contraction is significantly higher for the new binder material, 2% compared to 0.5-1% for the usual cement paste. This contraction can lead to unwanted cracking and deformation.

The volume contraction is due to the fact that water is consumed during chemical structure formation and that the reaction products formed have a smaller volume than the components from which they are formed. This leads to internal cavities and thus internal fluid bodies leading to tensile stresses in the liquid phase which compress the powder mass. The finer the powdery material, the higher the meniscus-induced tensile stresses and thus the contraction forces. Therefore, when powders which are 50 to 100 times finer than cement are used, substantially greater contraction forces prevail than in conventional cement paste.

This is e.g. known from desiccation of soil, where fine clay shows a clear volume contraction, while coarse sand does not significantly change its volume. The volume contraction is also heavily dependent on the hydration products formed, e.g. calcium silicathrate, during curing, especially their ability to form internal contract 53

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tension when less heavily bound water is moved to be consumed elsewhere in the hydration process.

Various precautions can be used or proposed for reducing or eliminating the volume contraction of the binder, reducing the volume contraction of the composite and / or reducing or eliminating possible deleterious effects of the volume contraction of the binder, especially the cracking.

1) Changing the liquid-gas interface tension and / or between liquid and solid to reduce the gas-liquid surface tension and / or to increase the contact angle in order to decrease the contraction forces. This can be achieved by adding surfactants or by changing (raising) the temperature.

2) Addition of liquid as compensation for liquid consumed by chemical reaction. Liquid is added from the outside to the surface of the article or from the inside through channels from an external source or from internal sources where the liquid may be present in liquid state (e.g., in porous sand or stone grains or in fibers) or in solid state (e.g. for example, as ice that melts later) or chemically bonded (so that the liquid is released, for example, by chemical or thermal influence).

3. Changing (increasing) the volume of the pore fluid to compensate for the chemical fluid loss, e.g. by heating. (Normally, the thermal volume changes in liquids are substantially greater than 25 in solids).

4. Reducing the volume contraction of the composite by using a dense pack of rigid coarse particles - typically sand and rock. Thus, the volume contraction in mortar and concrete will typically be reduced to a 1/10 compared to the pure paste.

5) Preventing the formation of internal cracks caused by the contraction tendency at 54

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(a) increasing the energy required to open a crack, e.g. by using sharp-edged sandstone materials and / or fibers and other reinforcement (the applicant has successfully used fine wollastonite fibers, various glass fibers, steel fibers and plastic fibers); b) increasing the stiffness of the composite material, e.g. using dense packing of sand and stone.

(The reason for both of these measures is the fracture mechanics since the fracture stress according to linear elastic fracture mechanics is proportional to the square root of the cracking energy multiplied by the modulus of elasticity.) C) Avoid incorporation of bodies which due to their size, shape or surface configuration would could act as an internal crack initiator and would be able to act as "leaders" of already formed cracks, as would be the case with e.g. large bodies with smooth surfaces.

6) Avoid damaging the body during the cure. This can be done, for example. is achieved by performing the cure in an area of compressive stress and / or by ensuring uniform contraction of the article, e.g. by appropriate mold design (the use of flexible molds of caustic and similar materials).

7) Providing a more volume-stable chemical structure 25 of the hydration product, e.g. by incorporating more calcium-rich ultrafine particles such as calcium carbonate particles, in accordance with what is described in the section below "The use of ultrafine particles to improve the chemical structure of DSP materials".

30 8) For heat cure (low pressure vapor cure or autoclave ring).

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9) When using components that consume less water during the hydration process, e.g. using cements with less C3A content than usual.

10) When using expanders such as aluminum powder which will compensate for the contraction by expanding simultaneously with the contraction. Other typical cement expanding agents may also be used.

APPLICATIONS

Because of its extreme density and mechanical strength, the material made possible by the present invention is applicable to a wide variety of articles, and examples of these articles are sheets or sheets of thin-walled or corrugated form, e.g. sheets or sheets of the same form as the known asbestos cement products; A cord; a tube; a refractory liner (e.g., applied as a complete liner) or a refractory liner component (such as a building block for a refractory liner); a protective coating (e.g. protection of other materials against chemical influences) such as a cheap protective coating applied to steel, e.g. such as steel pipes or conduits or on ordinary concrete products to give the concrete products a noble surface that is 20 strong and abrasion resistant and which acts as a seal against environmental impact, protective coatings on masonry, sidewalks and roads utilizing the same favorable properties of the new materials and protective coatings on roof panels or containers; a roofing material such as roofing sheets or tiles; an electrical insulating body; a shield for radioactive radiation for protection against radioactive impact (for the construction of reactors based on radioactivity, etc.), a seabed structure for deep water use; a machine part; a sculpture; A container; an oil bore hole wall molded in situ; or a supporting part of a building structure utilizing the extreme strength properties of the material and its resistance to climatic stresses, such as a beam, shell or pillar, typically as reinforced concrete, especially prestressed concrete.

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A further aspect of the invention relates to the use of a composite material containing Δ) inorganic solid SiC₂-rich particles of about size.

50 Å to approx. 0.5 µm, 5 B) solid particles of the order of 0.5-100 µm, which particles are at least one order of magnitude larger than the corresponding particles mentioned under A), with at least 20% by weight of the particles being Portland cement particles and wherein the amount of particles A is 5-50% by volume of the total 10 volumes of particles A + B, C) compact shaped solid particles of a material with a strength exceeding the strength of ordinary sand and rock used for ordinary concrete, typically a strength corresponding to at least one of the following criteria: 1) a piston pressure exceeding 30 MPa at a degree of packing of 0.70, above 50 MPa at a degree of packing of 0.75 and above 90 MPa at a degree of packing of 0; 80, determined by the method described herein (on particles of a material having a size ratio of the largest to the smallest particle substantially not exceeding 4), 2) a compressive strength of a composite material in which the particles are enclosed in a specific matrix exceeding 170 MPa (in the case of a substantial amount of the particles being greater than 4 mm) and 200 MPa (in the case of substantially all particles being less than 4 mm), determined by the 3) a Moh hardness (for the mineral composed of the particles) exceeding 7, and 4) a Knoop indentor hardness (for the mineral comprising the particles 30) exceeding 800;

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57 in that these particles have a size of 100 μπι-0.1 meters of water in a weight ratio of water to particles A + B of 0.12-0.30, and a concrete superplasticizer, the amount of super-plasticizer agent being in the range 1 -4%, based on the total weight of particles A + B, wherein the amount of particles B corresponds substantially to the tight packing thereof in the composite material with homogeneously packed particles A in the space between particles B, the amount of water substantially corresponds to 10 the amount needed to fill the space between particles A and B and the amount of concrete superplasticizer is sufficient to impart a liquid to plastic consistency to the composite material in a low stress range of less than 5 kg / cm 2, preferably less than 100 g / cm 2, and optionally D) additional bodies having at least one dimension at least one order of magnitude larger than the particles A for the manufacture of shaped articles selected among the group consisting of in situ cast oil boreholes; kanaludfyldninger; crack fills; sheets, slabs and roof tiles of thin-walled or corrugated form; anti-corrosion protection coatings applied to steel and concrete bodies; wires; tube; electrical insulating bodies; shielding from radioactive radiation; seabed structures for deep water use; brake linings; grinding aggregates; containers; machine parts; and sculpture tours.

A further aspect of the invention relates to a method of making a shaped article selected from the group consisting of in situ cast oil well casings; kanaludfyldninger; revneudfyldninger; sheets, slabs and roof tiles of thin-walled or corrugated form; anti-corrosion protection coatings applied to steel and concrete 58

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bodies; wires; tube; electrical insulating bodies; shielding from radioactive radiation; seabed structures for deep water use; brake linings; grinding aggregates; containers; machine parts; and sculptures; which method is characterized by combining A) inorganic solid SiC> 2-rich particles of a size of approx.

50 Å to approx. (B) solid particles of the order of 0,5 to 100 μπι, which particles are at least one order of magnitude larger than the 10 corresponding particles mentioned under A), with at least 20% by weight of the particles being Portland cement particles; and wherein the amount of particles A is 5-50% by volume of the total volume of particles A + B, C) compact shaped solid particles of a material having a strength greater than the strength of ordinary sand and rock used for ordinary concrete. , typically a strength corresponding to at least one of the following criteria; 1) a piston pressure exceeding 30 MPa at a degree of packing of 0.70, above 50 MPa at a degree of packing of 0.75 and above 90 20 MPa at a degree of packing of 0.80, determined by the method described in the following description ( particles of a material having a size ratio of the largest to the smallest particle substantially not exceeding 4), 2) a compressive strength of a composite material, the particles being enclosed in a specific matrix exceeding 170 MPa (i if a substantial amount of the particles is greater than 4 mm) and 200 MPa (in the case of substantially all particles being less than 4 mm), as determined by the method described herein, 3) a Moh hardness (for the mineral of the particles) exceeding 7, and 59

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4) a Knoop indentor hardness (for the mineral made up of the particles) exceeding 800, these particles having a size of 100 / η-0.1 m, • water in a weight ratio of water to the particles A + B 0.12-0.30, and a concrete superplasticizer, the amount of super-. plasticizer solids are in the range of 1-4%, based on the total weight of particles A + B, the amount of particles B being substantially equivalent to tight packing thereof in the composite material with homogeneously packed particles A in the space between particles B, the amount of water substantially corresponds to the amount needed to fill the space between particles A and B, and the amount of concrete superplasticizer is sufficient to impart a liquid to plastic consistency in a low stress area of less than the composite material. 5 kg / cm 2, preferably less than 100 g / cm 2, and optionally D) additional bodies having at least one dimension that is at least one order of magnitude larger than particles A, 20 by mechanically mixing the particles A, the water and the concrete superplasticizer; together with particles B and C and optionally additional bodies D until a viscous to plastic mass is obtained, and then, if necessary or if desired done, the resulting mass combines with particles and / or bodies of the above type (B, C, 25 D) by mechanical means to achieve the desired distribution of the components, and finally, the resulting mass in the desired shape molds in a region of low voltage, possibly incorporating, during casting, additional particles C and / or additional bodies D.

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Seabed structures for deep water use, e.g. Round containers that must withstand high hydrostatic pressure require high strength concrete, high durability and low permeability.

"Polymers in concrete", ACI Publication SP-40-1973, P 119-148, applies model experiments with small round shells with diameter approx. 40 cm, which is made of high quality polymer impregnated concrete and which is intended for deep water use. Complete impregnation is achieved by a complicated drying-vacuum gas removal in vacuum-printing method, which is limited in practice to small-sized objects. With the materials and methods of the present invention, it is possible to produce such large scale structures (with a diameter of several meters) with a similar high quality material by a simple fabrication technique.

Some examples of the use of DSP-15 materials have already been given above. Other materials are the following structures which can be made up against or between surfaces:

Large electrical insulators are today made of glass or ceramic materials, especially because of the excellent insulating properties of these materials. It is especially important to prevent flows along and along the surface layers. Furthermore, large insulators should have high mechanical strength and 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" to reinforcement (because they are formed from liquid masses at high temperatures and solidify under relatively large volume changes). However, in accordance with this aspect of the present invention, high material strength and good ability to absorb mechanical energy of such large electrical insulators can be obtained by producing large hollow shells or shells of glass or ceramic which are reinforced with high quality reinforced DSP 30 concrete, mortar or paste made by casting a soft mass (injection, etc.); the reinforcement may be pre-arranged in the interior of the sheath or shell (large steel bars, etc) or the reinforcement may be part of the casting material (e.g., chopped fibers).

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It is envisaged that this will enable cheaper production of large insulators in the sizes in which they are manufactured today, and to produce much larger insulators than those known today.

5 Furniture, shelves, doors, etc., which, due to the demands made on them in terms of appearance, touch, cleanliness, chemical durability, etc., require special surface properties combined with good mechanical material properties (strength and toughness). can be made from hollow bodies of plastic, metal and the like (e.g.

10 prepared by extrusion), which is filled with a reinforced DSP binder by pouring, injection, etc.

Safes and other strong containers which can be made by filling the cavities in doors and walls with the DSP material by molding a soft mass (injection, etc.); the inner reinforcement and hard coraponents (bauxite bricks) may be pre-arranged in whole or in part.

Containers for radioactive waste in which the radioactive waste is molded into the above-mentioned strong materials by injecting a paste or mortar of the DSP materials into the container space, in which all or part of the reinforcement, the radioactive waste in solid form and various stiffness message elements (e.g. bauxite stones) have been pre-arranged.

Very large sculptures of desired surface materials which can in a cheap way be given the necessary mechanical strength by filling a thin shell with reinforced mortar or concrete made in accordance with the principles mentioned in the above examples.

Supporting structures with special requirements for surface materials (columns, walls, floors, roof elements, etc.)

Ship hulls with an exterior and interior of materials with special properties (eg smooth exterior and heat insulating interior) where the required part is filled with reinforced DSP concrete, mortar or paste by injection etc.

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Pipes with an exterior and an interior comprising material with special properties (eg acid-resistant interior and heat insulating exterior), where the space between the pipe walls is filled with reinforced DSP concrete, mortar or paste by injection etc ..

5 As mentioned above, there are a number of advantages and potential benefits associated with the separate manufacture of hollow shells, which are filled in whole or in part with the DSP materials. In this context, it should be emphasized that e.g. can be made of very large thin-walled bodies with monolithic reinforced core. It is e.g. it is possible to produce long stretches of pipes with monolithic strong reinforced core in the pipe walls (eg in connection with pipelines on the seabed, where pipes with hollow plastic walls or the like are placed correctly, the space is filled with stones and reinforcement and the pipes are filled with DSP paste or mortar by injection).

15 Other items that can be manufactured in this way are ship hulls, large building elements, tunnel linings and the like.

The ability to produce reinforced concrete, mortar and paste with very high strength and acceptable toughness with a simple molding technique and at room temperature makes it possible to produce articles traditionally made of metal. Such objects are especially large load-bearing parts, which are traditionally manufactured in metal casting (covers, lids, large valves, load-bearing machine parts, etc.) and structural elements (masts, beams and the like).

The high hardness of the DSP materials, combined with the fact that they can easily be made cool by fiber reinforcement, make it possible to use the materials as grinding or crushing bodies and abrasive aggregates, typically made by the usual casting of a soft mass, extrusion or compression.

A further aspect of the invention relates to a shaped article which is characterized in that it comprises a continuous matrix, 63

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which matrix comprises A) homogeneously arranged inorganic solid SiC 50 Å to approx. 0.5 mm, or a coherent structure formed from such homogeneously arranged particles, B) tightly packed solid particles of the order of 0.5-100 μια and at least one order of magnitude larger than the respective particles mentioned under A), or a coherent structure formed from such tightly packed particles, at least 20% by weight of the particles being Portland cement particles, the particles A or the coherent structure formed therefrom being homogeneously distributed in the space between the particles B, and the amount of particles A being 5-50 volumes -15 percent of the total volume of particles A + B, and the dense package being essentially a package similar to that obtainable by gentle mechanical action of a system of geometrically similar shaped large particles, where locking surface forces have no significant effect, a concrete superplasticizer, the amount of superplastic lubricant solids are in the range of 1-4%, based on the total weight of the particles A + B, and further include, embedding in the matrix 25 C) compact shaped solid particles of a material exceeding the strength of ordinary sand and stones used for ordinary concrete typically have a strength corresponding to at least one of the following criteria: 1 a piston pressure exceeding 30 MPa at a packing degree of 30 0.70, above 50 MPa at a packing degree of 0.75 and above 90 64

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MPa at a packing rate of 0.80, determined by the method described herein (on particles of a material having a size ratio of the largest to the smallest particle substantially not exceeding 4), 5 2). 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 the case of substantially all particles being smaller 3) a Moh hardness (for the mineral made up of the particles) exceeding 7, and 4) a Knoop indentor hardness (for the mineral made up of the particles) (d) additional bodies having at least one dimension that is at least one order of magnitude larger than particles A, the shaped article being has been prepared using a weight ratio of water to particles A + B of 0.12-0.30, further comprising one or more surface layers having a substantially uniform thickness and a structure different from the oven for defined structure adjacent to the surface layer (s).

A further aspect of the invention relates to a method of making an article according to any one of claims 57-60, which is characterized by combining 65

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A) inorganic solid SiC4-rich particles down to a size of from ca. 50 Å to approx. 0.5 μπι and B) solid particles of the order of 0.5-100 μπι, which particles are at least one order of magnitude larger than the respective particles mentioned under A), with at least 20% by weight of the particles being Portland cement particles, and the amount of particles A being 5-50% by volume of the total volume of particles A + B, water in a weight to water ratio of particles A + B of 0.12-0.30, and a concrete superplasticizer, plasticizer solids are in the range of 1-4%, based on the total weight of particles A + B, the amount of particles B being substantially equivalent to tight packing thereof in the composite material with homogeneously packed particles A in the space between particles B, the amount of water substantially corresponds to the amount needed to fill the space between particles A and B, and the amount of concrete superplasticizer is sufficient to give the composite a flow to a plastic consistency in a low voltage range of less than 5 kg / cm 2, preferably less than 100 g / cm 2, and C) compact shaped solid particles of a material having a strength exceeding the strength of ordinary sand and rock, 25 used for ordinary concrete, typically a strength corresponding to at least one of the following criteria: 1 a piston pressure exceeding 30 MPa at a packing rate of 0.70, above 50 MPa at a packing rate of 0.75 and above 90 MPa at a packing rate of 0.80, determined by the method described in the present description (on particles of a machine 66

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material having a size ratio of the largest to the smallest particle substantially not exceeding 4), 2) a compressive strength of a composite material, wherein the particles are enclosed in a specific matrix exceeding 5 170 MPa (in case a substantial amount of the particles is greater than 4 mm) and 200 MPa (in the case of substantially all particles being less than 4 mm), determined by the method described herein, 3) a Moh hardness (for the mineral, the particles consist of 10) exceeding 7, and 4) a Knoop indentor hardness (for the mineral of the particles) exceeding 800, these particles having a size of 100 μπι-0.1 m, and optionally 15 D) additional bodies having at least one dimension at least one order of magnitude larger than particles A, by mechanically mixing particles A, water and concrete superplasticizer with particles B and C and optionally additional particles D until reached a plastic mass viscose, and then, if necessary or desired, combines the resulting mass with particles and / or bodies of the above type (B, C, D) by mechanical means to achieve the desired distribution of the components, and Finally, the resulting mass contacts one or more layers, having a structure different from the cured structure of the resulting mass, in a low voltage region, optionally with incorporation, during casting, of particles C and / or bodies D, and cures the molded mass in such a way that the layer or layers are integrated with it 67

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cured mass so that it or they form one or more surface layers covering the mass.

For the purposes of the patent claims relating to this section, we should note that the term "substantially uniform thickness" is not to be construed as a limitation to particular surface layers of very precisely controlled thickness. The term "substantially uniform thickness" merely indicates that these are not structures which can no longer be reasonably referred to as surfaces or surface layers, e.g. a rock structure where a cavity has been filled with the DSP mass.

The indication that the surface layer (s) must have a structure different from the structure of the cured mass cast against or between the surfaces must reflect the fact that the outer material is different from the inner material which 15 is reversed in that case. It is absolutely not excluded that the type of material used for the outer surface is of the same type of material used for the inner material, in other words, contains a matrix of the same type.

PRESSURE FOR DSP

20 A particularly promising method for making articles with DSP is the printing molding of DSP materials with plastic to rigid plastic consistency.

This is a fast process which requires substantially less molding material than usual molding, and which enables the production of products of substantially higher quality than can be obtained in conventional molding, given that the water / powder ratio is substantially lower in molding (typically 0.08 - 0.13 as opposed to 0.20 in the usual casting of cement / silica paste-based articles), which allows the incorporation of multiple fibers and finer fibers into the pressurized masses 30 ( of plastic cement / silica paste using up to 6 volume percent glass fibers with a diameter of 5 μιη and length 12 mm).

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Before the molding, a semi-finished product is formed, which becomes the finished object after the pressure treatment. The semi-finished product is formed by mixing processes and various forms of pretreatment (e.g. extrusion or rolling) to ensure a desired fiber orientation and a desired starting form of the semi-finished product.

The semi-finished product is placed in a press, a rolling mill or the like, if the surfaces facing the semi-finished product ensure that the compressed articles get the desired shape. Examples are shown in FIG. 24 - 28.

By moving one or more parts of the printing tool, the material 10 is pressed into the cavity and thus forms the desired object with the desired shape.

Upon removal from the printing surfaces, the forming article can be removed from the press, being supported to a greater or lesser extent by mechanically stable molds; the requirements for these stabilizing molds depend on the mechanical stability of the pressurized material, the geometry (size and shape of the object), external influences after the printing (gravity, vibration, etc.) and requirements regarding the dimensional and shape tolerances of the object.

Semi-finished 20 In this context, the term "semi-finished" refers to the bodies which are converted into press-shaped objects by pressure treatments.

The semi-finished articles can be formed from the components described above (particles, fibers, other components, liquids, etc.) and can also be formed by one of the processes described above for forming the finished article (extrusion, rolling, vibrating, spraying , etc.), or by molding (when production is made by consecutive molding operations.

The semi-finished products can be made from various sub-components which, during the printing operation, are formed to form a continuous product. Thus, e.g. plate shaped articles with specific fiber

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69 arrangements are made by placing layers of thin extruded sheets (with the fibers substantially oriented in the extrusion direction) in appropriate and desired orientation relative to each other, as illustrated in FIG. 25, and articles which it is desired to incorporate, e.g. electrical resistance units, pipes, cables, sockets, reinforcements, etc., or various other components (steel sheets, wooden bodies, etc.) can be embedded in the finished article in the molding, as illustrated in FIG. 24 - 27.

Pressure Treatment 10 As mentioned above, the pressure treatment is carried out by moving one or more parts of the printing tool in relation to the material to be formed, thus pressing the material into the desired shape.

Often, the molding cavity is completely closed and the material is filled to fill this entire cavity by being pressed against the non-elastic mold sides. This is a pressing process.

In other cases, the pressure treatment is performed in cavities which are not completely closed on all sides. An important example of this is the process of pressure treatment, which is termed extrusion, where the material is pressed out of an orifice of a certain cross-section, leading to an object of this cross-section, or an embossing, which is often a local pressure forming.

A particularly interesting technique is rolling with flexible rollers.

As mentioned above, no extrusion of liquid from the workpiece to the environment will normally occur, which is one of the major advantages of the DSP molding mass.

However, using drainage pressure treatment, it becomes possible to construct a new type of coarse component materials (large in comparison to particles B) placed in dense packing similar to what can be achieved with the components involved in a printing process (possibly vibro pressing). glued together using high quality DSP-30 paste.

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The sample consisting of the coarse components is pressed in one of the following ways: 1) With an excess of liquid paste (eg cement silica DSP paste with water / powder ratio of 0.20) which is pressed out of the blank, suitable filter or drainage means placed in the press (cf. Figs. 15, 16 and 17), 2) are used with less than the final proportion of liquid paste - possibly without any liquid paste at all, the liquid paste being added by pressing , capillary suction, vacuum suction or similar means in a later process or during the pressure treatment; 3) with an amount of liquid paste corresponding to the proportion thereof in the finished product.

In the former case, the pressure treatment as mentioned above is accompanied by the pressing of a liquid material. The pressure treatment apparatus 15 is arranged so that it is capable of draining the extruded liquid without in any significant way interfering with the printing process.

By using processes of this kind, it becomes possible to produce articles of good stability immediately after the pressure treatment.

Final treatment 20 After the molding, a blank having a more or less stable shape has been formed. Depending on the stability, different degrees of support of the workpiece may be used: 1) Support at the bottom or elsewhere solely for the purpose of placing the specimen in a desired position (support may be, for example, a floor or shelf), 2 the support along essential portions of the shaped surface to maintain the shape of the fabricated article, 71

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3) complete support around the full surface of the blank to maintain the shape of the manufactured blank.

The workpiece and support means may be combined in the press, a portion of the forming surface being a mold which, after printing treatment 5, accompanies the workpiece as mold support (the molds may, for example, be thin pressurized metal bodies), or contacted with the workpiece. a separate process after the subject has left the press.

In many cases, the pressurized blank is surface-treated immediately after the pressurization, first and foremost to avoid drying out 10 upon further treatment.

The surface treatment can be carried out by applying curing compounds to avoid evaporation, which e.g. can be done by brushing, lubrication, spraying, etc., or by applying evaporative-preventable removable film after leaving the press or in connection with the pressure treatment process by transfer from the forming surfaces of the press.

In many cases, the aforementioned supports may also be utilized for the application of a surface treatment, or they may render the surface treatments redundant, or the support may constitute the surface treatment (e.g., a ceramic shell applied in the press).

Finally, the pressure treatment can be accompanied by processes that ensure that the sample somehow transitions to solid state - in addition to the transition to solid state that results from the pressure itself. Examples include the simultaneous application of heat (by heat transfer from the press or by electric or microwave heating) or triggering of polymerization of a polymerizable component incorporated in the liquid phase.

A cement / water-based DSP composite material may be retarded for its chemical structure formation and / or stabilized for its form by freezing the DSP composite material or semi-finished product. In this way, the composite or semi-finished material can be mixed or formed in advance and then transported 72

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to a desired application where the structure formation process may be allowed to proceed by thawing the product, possibly in combination with subsequent molding. This method can generally be applied to any type of DSP material where the structure formation 5 can be delayed, retarded or interrupted by freezing or a similar process. The DSP material subjected to this process can be formed in advance in any of the ways described herein.

FORMING DSP IN A HIGH VOLTAGE AREA

Forming of DSP materials can also be carried out in a high voltage range, typically between 5 and 100 MPa, in special cases between 100 and 1000 MPa, and in extreme cases between 1000 and 10000 MPa.

The high voltage molding will usually be combined with a prior molding of the lower voltage DSP material, typically 15 to obtain 1) an approximate form of articles, and 2) a desired arrangement of particles, fibers, etc., before the final forming in a high voltage area.

The molding in a high voltage region can typically be used during solidification, e.g. by hot or cold pressure sintering, or - what is typical of cement products - by structure formation during hydration.

By forming in a high voltage region, closer structures are obtained. It is known to form objects in high voltage regions by powder compression, pressure sintering, etc., but by all these known methods it is not easy and in most cases not possible to obtain a desired predetermined microstructure. Using structure forming techniques of the present invention in a superplasticized material in a low voltage region, the desired particle / fiber arrangement can be determined in advance and

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The high voltage operation can be performed on the structure thus arranged in advance.

Articles typically produced by molding in a high voltage region are e.g. high voltage machine parts, aircraft or spacecraft parts subjected to extreme mechanical loads and other objects subjected to harsh conditions during their use, including high fiber content combining extreme resistance and hardness with high tensile strength and ductility.

A particularly interesting technique is to combine the molding in a high voltage region with various pre-arrangement methods described in the "PRESSURE FOR DSP" sections. The various production methods comprising semi-finished products described in this section may conveniently be combined with a finishing of the semi-finished products in a high voltage area.

In particular, the forming of DSP in high-voltage areas allows high hardness and abrasion resistance to be combined with a high degree of ductility (obtained with a high fiber content), which are properties which are usually very difficult to combine using 20 known techniques.

A DSP composite material and / or a DSP semi-product can be formed in a high voltage region, typically a range of 5 - 100 MPa, in special cases 100 - 1000 MPa and in extreme cases 1000 - 10,000 MPa. A cement-based DSP material can also be converted to solid form 25 with a high voltage level, typically 0-5 MPa, e.g. curing between plates in a press. In special cases, the curing can be carried out at higher stress levels, such as 5 - 100 MPa, and in very special cases at stresses between 100 and 1000 MPa or even between 1000 or 10,000 MPa.

If desired, the cure in a high voltage region can be combined with the DSP composite material prior to molding being treated under high shear conditions, e.g. by optionally repeated passage through multiple roll systems in accordance with the technique described 74

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in European Patent Application No. 80301909.0, published under publication number 0 021 682.

»'V *' - 75

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Example 1.

The following materials were used in the Examples:

White Portland cement: Specific surface (Blaine) 4380 cm2 / g.

Room weight (expected) 3.15 g / cm3.

Silica dust: Fine spherical Si02 * rich dust.

Specific surface (determined by BET technique) approx. 250,000 cm 2 / g, corresponding to an average particle diameter of 0.1 μ. Room weight 2.22 g / cm3.

Bauxite: Refractory calcined bauxite, 85% AI2O3, bulk weight 3.32 g / cm3 for sand 0-4 mm, 3.13 g / cm3 for rock 4-10 mm.

Mighty®: A so-called concrete superplasticizer, sodium salt of a highly condensed naphthalene sulfonic acid / formaldehyde condensate, 20 of which typically consists of more than 70% of molecules with 7 or more naphthalene nuclei. Room weight approx. 1.6 g / cm3. Available either as a solid powder or as an aqueous solution (42% by weight

Mighty®, 58% by weight water).

Water: Plain tap water.

Preparation of cylindrical concrete samples from wet concrete mixed with silica / cement binder and calcined bauxite sand and stone: -31: 76

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The concrete samples are prepared from one batch of 23 liters with the following composition:

Silica dust: 3200 g

White Portland cement: 16000 g 5 Bauxite 4-10 mm: 32750 g

Bauxite 0 - 4 mm: 10900 g

Mighty® (powder): 250 g

Water: 2980 g

Mixture 10 Coarse aggregate, cement and Mighty® powder are dry mixed for 5 minutes in a 50 liter bucket mixer. Then the silica dust is mixed and the mixture is continued for 10 minutes.

Fresh concrete

The concrete is soft and easily workable.

15 Molding 6 concrete cylinders, diameter 10 cm, height 20 cm, and 2 slabs (40 x 30 x 5 cm) are cast at 20 ° C. The sample is vibrated for 10 - 30 seconds on a standard tea table (50 Hz).

Curing 20 Immediately after casting, the closed molds are immersed into the cylinders in water at 60 ° C and cured for 5 days. The plates are covered with plastic film and cured for 1 day at 20 ° C in the air, then immersed in water at 60 ° C and cured for 4 days. After curing, samples are removed from the mold and stored in air at 20 ° C and ca. 70% relative humidity until the 25 is tested (the test is done before a period of 30 days after the heat treatment).

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testing

Room weight, sound velocity, dynamic modulus of elasticity, compressive strength and stress / strain curve are determined for the 6 concrete cylinders (stress / strain curves are only determined for 2 samples).

5 The test results are shown in Table 1 below.

Table 1

Properties of hardened concrete

Room weight Sound speed- Dynamic elastic Compressive force Static heat modulus elasticity modulus 2878 kg / m3 6150 m / sec. 109000 MPa 217.5 MPa 78000 MPa (standard deviation 15 6.2 MPa)

Example 2

Various concrete superplasticizers are being tested to determine the water requirement for obtaining the liquid to plastic consistency of the pulp to be cured.

The following superplasticizers (SPT) are used:

Mighty®: See Example 1.

Lomar-D: A concrete superplasticizer of the same composition 25 as Mighty®, made of 78

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Diamond Shamrock Chemical Company, N. Jersey, USA.

Melment®: An anionic melamine resin solution.

5 Betokem®: A sulfonic acid formaldehyde condensate based on naphthalene and lignosulfonate.

Sycamore: A sulfonic acid-formaldehyde con - densate based on naphthalene.

10 In all series, the following common components are used (calculated on one charge):

Quartz sand 1 - 4 mm 2763 g

Quartz sand 0.25 1 mm 1380 g

Quartz sand 0 - 25 mm 693 g Portland Portland 2706 g

Silica dust 645 g of SPT amount is determined so that the dry matter content is at least 82 g per liter. mix. A somewhat higher dosage is used with Betokem® and Sikament.

The following components are different:

Series 1: Mighty® solution (42%) 195 g

Additional water 437 g

Series 2: Lomar-D solution (37%) 221 g

Additional Water 461 g 25 Series 3: Melment® Solution (20%) 410 g

Additional water 322 g

Series 4: Betokem® solution (38%) 273 g

Additional Water 431 g 79

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Series 5: Sycamore solution (42%) 234 g

Additional water 464 g

Mix

The mixture is carried out in a planetary kneading machine using a mixing bucket. The following procedure is used: 1) Dry mix of sand, cement + filler for 5 minutes.

2) Adding most of the water which does not form part of the concrete superplasticization solution. Ca. 50 ral of the water is retained for later use as rinsing water. Continue mixing for 5 minutes.

3) Adding the concrete superplasticizer solution and subsequently rinsing the container with the above 50 ml of water to ensure that all the concrete superplasticizer is incorporated into the mixture. Mix for approx. 10 minutes.

15 The water needs, ie. the amount of water used in the various mixtures to obtain the specified consistency is determined by test mixture. Water requirements are shown in Table II below.

The consistency is assessed by measuring the spread of a cone of the material formed by pouring the material into a 5 cm high brass cone shape with bottom diameter 10 cm and upper diameter 7.1 cm on a floating table with brass surface for use of hydraulic cement ( ASTM C 230-368) and remove the mold. The diameter of the material is measured a) immediately after removal of the mold, b) after 10 shocks and c) after 20 shocks.

The consistency is considered to be of the desired value for diameters of approx. 12 cm after 10 shocks and 14 cm after 20 shocks.

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Table II

Water requirements (including water in the superplasticizer solution) expressed in grams of water per charge and in relation to the total amount of fine powder (cement + silica dust) by weight, the volume of fine powder being the same in all the mixtures (1160 cm 2).

Type of plasticizer Water requirement gram weight ratio water / cement 10 + silica dust

Mighty® 550 0.16

Lomar-D 550 - 600 0.16-0.18

Melment® 650 0.19 15 Betokem® 550 - 600 0.16 - 0.18

Sickness 550 - 600 0.16 - 0.18

Comments on the test results

The tests can be compared to the tests mentioned in Example 7 20 in International Patent Application No. PCT / DK79 / 00047, Series 1, Table V. The amounts of sand, cement and silica are the same as in the example, but the silica dust and cement originate. from later charges. Another difference is that in Example 7 of International Patent Application no.

PCT / DK79 / 00047 used Mighty® powder, which was dissolved immediately before mixing, while in the present experiment a

Mighty® solution supplied by the manufacturer. It should be noted that the water requirement in all cases with high dosage of superplasticizer is low, namely in the range of 500 g in Example 7 of International Patent Application No. PCT / DK79 / 00047 to 600 - 650 g for Melment® in the present trials, corresponding to water / powder ratio of 0.15 - 0.19 by weight. This should be compared to 1200 g of water and water / powder ratio of 0.36 in the mortar without superplasticizer. It should be 81

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It is noted that there are minor differences between the water needs of the different types of superplasticizers and that Mighty ^ is among the best. However, all of the superplasticizers are found to lead to the extremely good flow properties of the very low water content cement + silica dust binder characteristic of the materials of the present invention and according to International Patent Application No. PCT / DK79 / 00047.

Example 3

Powder compression of sand and rock 10 The purpose is to evaluate the resistance of various sand and stone materials to deformation in the powder compression, especially to compare natural concrete aggregates with particularly strong and hard materials.

Materials 15 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 frame, (qual. 10 / F PS - K Arendal Smelter Works A / S, Ejderihavn,

Norway).

Comments 20 The individual fractions of particles are relatively uniformly graded, corresponding to the fact that the ratio of the largest to the smallest grain size (particle size) does not substantially exceed 4.

powder Compaction

Samples of the individual sand and rock fractions are compressed by uniaxial pressing in a mold. The pressing apparatus consists of a cylindrical mold cylinder which is open at both ends and two cylindrical pistons (diameter of mold cylinder 30 mm, powder height at filling about 32 mm and after compression 16 - 23 mm, depending on the type of powder).

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The dry materials are loosely poured into the mold cylinder. The compression is carried out in an Instron test apparatus at a constant compression rate (5 mm / minute) up to a compression pressure of 350 MPa, after which the pressure is relieved by moving the piston in the opposite direction. During compression and relief, force / displacement curves are recorded.

results

From the force / displacement curves, comparisons of the compression pressure are made to obtain identical "density" for the individual materials. The results are shown in Table III.

Table III

Compression pressure, MPa, as a function of the degree of compression. The degree of compression is the ratio of the volume of the particles to the volume of the total powder mass (expressed in another way: 1 - porosity).

Compression Granite Quartz Quartz Bauxite Bauxite Silicon grade 4-8mm l-4mm 0.25-lmm 4-10mm 0-2mm umcarbide 0.5-2mm 0.70 16 10 24 36 61 48 0.75 29 23 42 61 110 82 20 0.80 59 43 76 95 194 145

It should be noted that the compaction pressure required to achieve the same degree of compaction is substantially higher for the hard materials (bauxite and silicon carbide) than for the materials commonly used as concrete additives (granite and quartz). .

comments:

The powder compression technique is suitable for comparing the strength of particles, provided that the various particulate materials or particulates 83

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particle compositions have approximately the same particle geometry and provided that the particle size is relatively large in comparison with the dimensions of the mold cylinder. These conditions are reasonably met in the quartz sand and fine bauxite test (in these cases the particles are compact, rounded and small). In the granite and coarse bauxite experiments, the particle / piston ratio is somewhat too large (about 0.2 - 0.3) to allow a direct comparison with the results of the quartz sand and fine bauxite experiment. On the other hand, a comparison between these two is reasonable. It is difficult to compare the results of the experiments with silicon carbide with the other results since, unlike all the other materials, this powder material has very sharp edges.

Example 4 High quality mortar Two different types of mortar are produced, both on the basis of low alkali sulphate resistant Portland cement, silica dust and Mighty®, but with different types of sand, namely refractory bauxite and silicon carbide (qual. 10 / F PS - K, Arendal Smelterworks A / S, Ejdenhavn, Norway). The purpose is to investigate the mechanical properties of mortar made with the very strong sand, cf. Example 3, and with the very strong silica / cement binder described in International Patent Application No. PCT / DK79 / 00047. In all the mixtures the following components (indicated on one charge) are used:

Silica dust 645 g 25 Low alkali, sulphate resistant

Portland cement 2706 g 42% Mighty® solution 195 g

The following components are used for the bauxite mortar:

Bauxite 0 - 4 mm 6104 g 30 Water (other than water in the Mighty® solution) 387 g 84

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The following components are used for mortar with silicon carbide:

Silicon carbide 5755 g

Water (other than water in

The Mighty® solution) 487 g 5 The amounts of sand, cement and Mighty® (by volume) used are the same as those used in Example 9 of International Patent Application No. PCT / DK79 / 00047. In the bauxite mortar, the amount of water is also the same as in Example 9 of International Patent Application No. PCT / DK79 / 00047, while the amount of water in the silicon-10 carbide mortar is somewhat higher. This is because the silicon carbide sand has very sharp edges and therefore requires a more fluid silica / cement paste and / or a larger volume of paste.

For each of the two types of mortar, two batches are prepared, one having a composition as indicated above and the other of twice the size.

Mixing and casting

The mixture is carried out in a planetary moving kneading machine using a mixing bucket. The following procedure is used: 1) Dry mix of sand, cement + filler for 5 minutes.

2) Adding the majority of the water which does not form part of the concrete superplasticization solution. Ca. 50 ml of the water is reserved for later use as rinsing water. Continue mixing for 5 minutes.

3) Adding the concrete superplasticizer solution and subsequently rinsing the container with the above 50 ml of water to ensure that all the concrete superplasticizer is incorporated into the mixture. Mix for approx. 10 minutes.

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The mortar mixtures behave like highly viscous liquids and are molded into cylindrical molds (height 20 cm, diameter 10 cm) on a standard rice tea table (50 Hz). The casting time is approx. 1 minute. The test bodies (in closed molds) are cured in water at 80 ° C for 4 days.

5 Testing

Density, sound speed, dynamic modulus of elasticity, compressive strength and tension / strain curve are determined. The compressive strength and stress / strain curves are determined on a 500 ton hydraulic press using a stress change rate of 0.5 MPa per liter. second. The results 10 are shown in Table IV:

Table IV

Properties of cured mortar judged by measurement on cylindrical specimen bodies (height 20 cm, diameter 10 cm).

Bauxite Mortar Silicon Carbide Mortar

Density (kg / m3) 2853 (6) *) 2640 (6) *)

Sound speed w / sec. 6449 (6) *) 6443 (6) *)

Dynamic Elasticity Module (MPa) 118600 (6) *) 109600 (6) *)

Compressive strength and its

standard release (MPa) 248.0 SD 7.7 184.3 SD

(6) * 5.9 (4) * 25 *) - number of tests.

The stress / strain measurements are performed on two test bodies from each series. Sample bodies are loaded to approx. 60% of their breaking load and then relieved, which in turn is charged to break without tension / strain detection. A few of the test bodies are loaded and unloaded several times.

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The stress / strain curve for the bauxite mortar is practically a straight line throughout the measurement range (0 - 150 or 160 MPa) with a slope (secant) corresponding to a modulus of elasticity of 84300 MPa. With repeated loading and unloading, only minor hysteresis is found.

5 The tensile / strain curves for the silicon carbide mortar (measuring range 0 - 100 MPa) deflect somewhat with an initial slope corresponding to a modulus of elasticity of 86000 MPa and an elasticity modulus at the pressure of 100 MPa of 72000 MPa. At repeated load of 100/120/140/160 MPa, a sample of the silicon carbide mortar shows marked hysteresis, suggesting internal structure degradation.

The compressive strength of bauxite mortars does not appear to be significantly affected by a preload of up to 150 - 160 MPa, whereas the strength of the silicon carbide mortar is substantially lower for the samples already loaded.

15 The values of the compressive strength of the samples already loaded with the silicon carbide mortar are therefore not included in the results in Table IV.

Comments on the results

It will be noted that the bauxite sand mortar is extremely strong and 20 rigid, with compressive strengths of 248 MPa (maximum value for two of the test bodies was 254.2 MPa, corresponding to a load of more than 200 tons). The fracture extends extensively through the bauxite tooth, which shows the possibility of making even stronger mortar by using even stronger sand materials.

The compressive strength of the silicon carbide mortar is substantially lower (184.3 MPa) and is not much higher than that of the corresponding mortar containing quartz sand (160 - 179 MPa, cf. International Patent Application No. PCT / DK79 / 00047, Example 9), which may seem peculiar given the great hardness and strength exhibited by silicon-30 carbide itself. The reason is undoubtedly that in the silicon carbide mortar substantially more water is used than in the bauxite mortar and the quartz sand mortar described in international 87

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Patent Application No. PCT / DK79 / 00047. This leads to a significantly weaker binder. The water / powder ratio (total weight of water versus cement + silica) is 0.149 for the bauxite or quartz mortar and 0.179 for the silica carbide mortar. The fracture extends extensively 5 outside the silicon carbide particles. This, in conjunction with the bent stress / strain curve and the large hysteresis (which is characteristic of brittle materials where the particles are significantly stronger than the matrix) suggests the possibility of obtaining significantly higher strength by improving the matrix. This can be achieved by reducing the water / powder ratio to e.g. 0.13 - 0.15, which is possible by using a somewhat coarser silicon carbide sand and / or greater amount of cement and silica.

An additional 16 cylinders of the bauxite mortar of the same composition have been made using the same technique as above except that the bauxite was from a later charge.

15 The purpose was to investigate various mechanical properties. First, the density, sound velocity and dynamic elastic modulus are determined for all 16 sample bodies. As a guide, the tensile strength is determined on two of the test bodies.

The results are as follows: 20 Density 2857 kg / m 2

Sound speed 6153 m / second

Dynamic modulus of elasticity 108200 MPa

Compressive strength 261.1 MPa 268.1 MPa 25 Comments on the test results:

The same density has been found as above, while the sound speed and dynamic elastic modulus are somewhat higher. The reason for this is not known, but is believed to be an error in determining the time of the sound pulse passage (either in the test on page 64 or in the test above 30).

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

Example 5

High quality bauxite mortar 5 A bauxite mortar of the same composition and using the same technique as in Example 4 has been prepared with the following exceptions: 1) the bauxite is from a later delivery, 2) the size of each charge is twice that used in Examples 4 and 10 3) the test bodies were allowed to stand for a few days and up to six months after the heat cure (4 days at 80 ° C) at 20 ° C at 70% relative humidity.

For each of the 4 loads, four cylinders are cast (height 20 cm, diameter 10 cm).

15 Testing

Density, sound velocity, dynamic modulus of elasticity and stress / strain curve are determined using the method described in Example 4.

The results are shown in Table V below.

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Table V

The properties of cured bauxite mortar determined by measurement on cylindrical specimen bodies (height 20 cm, diameter 10 cm).

Density kg / m ^ 2857 SD 8 (16) 5 Sound speed m / sec. 6153 SD 36 (16)

Dynamic elasticity module MPa 108156 SD 1426 (16)

Compressive strength MPa 268.3 SD 7.5 (14) 10 The stress / strain curve is shown in fig. 14 together with a corresponding curve for ordinary concrete, which is usually considered to be very high quality.

It appears that bauxite-cement silica mortar has a compressive strength (270 MPa) which is approx. four times higher than the compressive strength of traditional 15 high quality concrete and a modulus of elasticity (slope of the curve) of approx. 2 times the modulus of elasticity for traditional high quality concrete.

One of the samples has a compressive strength of 282.7 MPa and a density of 2861 kg / τα}, which corresponds to a stress / density ratio of 98812 (m / s) 2.

20 The cylinder load corresponds to the foundation load on a prism with height 10076 meters made of the material.

(By comparison, the sound load of high quality structural steel (400 PMa) corresponds to the foundation load of a 5200 meter high steel prism).

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The invention will now be described in more detail with reference to the drawing, in which Figures 1, 2, 4 and 5 show enlarged and sectional views of various DSP systems comprising tightly packed bodies; Figures 6 and 7 are enlarged and sectional views showing the behavior of cement particles in ordinary concrete; Fig. 8 is a further enlarged sectional view showing cement particles in DSP; Fig. 9 is an enlarged sectional view showing the anchoring of a reinforcing fiber in DSP matrix; Figure 10 is a sectional view showing the internal context of a DSP paste and its resistance to mixing with flowing water; Figure 11 is a sectional view of the use of DSP in practice for an otherwise difficult repair of a concrete structure under flowing water; Figure 12 in section shows the use of DSP in practice for repairing a concrete wall where there was only unilateral access to introduce the repair material. Figure 13 is a sectional view of the use of DSP's easy-flow properties to establish an inner DSP coating in a curved tube; 14 shows a stress-strain diagram for ordinary high-strength concrete and DSP containing refractory bauxite, respectively; 15 - 17 in section show compression with drainage of liquid, fig. Fig. 18 is a perspective view of the preparation of a plate-shaped body, which may be subjected to further molding; 19 and 20 show in perspective the forming of a portion of a tube of a plate-shaped body; Fig. 21 is a perspective view of the use of extrusion for the manufacture of DSP-encapsulated electrical components; 22 and 23 in section illustrate the use of DSP for molding as a plastic material; 24 is a perspective view of the manufacture of plate-shaped reinforced articles, e.g. wall or roof elements, by laying rolled sheets of DSP over each other, fig. Fig. 25 is a perspective view of the preparation of a sandwich element of two 35 sheets of rolled fiber reinforced material, the fiber orientation of one layer of the sandwich being perpendicular to the fiber orientation of the other layer; 26 shows in perspective the principle of the formation of a plate-shaped 91

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element of two plates between which there are sanitary installations or the like, fig. 27 is a perspective view of the lower element of an element similar to that shown in FIG. 26 but with incorporated piping 5 for underfloor heating or electrical installations; 28 is a perspective view showing the mass production of tiles or bricks or the like of a sheet of DSP; 29 'shows in section a material comprising small particles packed against larger bodies; Fig. 30 is a sectional view of the wall effect, with the packing density of the particles in the narrow zone near the wall being less than in the main mass; 31 in section shows the arrangement of particles in a cavity by sedimentation.

Reference is made to the drawing, wherein the same numbers generally refer to the same parts.

In FIG. 1, showing a typical DSP matrix structure, 10 and 12 denote substantially densely packed particles B, e.g. Portland cement particles, and 14 denote homogeneously arranged and optionally tightly packed particles A, e.g. silica dust particles which are homogeneously distributed in water by a concrete superplasticizer, or a coherent unit structure formed by such particles and of solid interparticle substance formed by chemical reaction between the solutes emanating from the cement particles. The system shown in FIG. 1, is typically established by delicate mechanical means, e.g. by shear or vibration, or simply under the influence of gravity.

1 FIG. 2, the particles B (12) comprise larger particles and smaller particles with leaping gradient between the particles B. The system of FIG.

2 is typically established using the same means as described in connection with FIG. First

In FIG. 1 and FIG. 2, however, 14 may also denote ultrafine particles which are homogeneously arranged by a surfactant in accordance with the methods for establishing the liquid DSP system of the invention, but which are now surrounded by a 92

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interparticle substance that differs from the fluid by which the particles are arranged and introduced by replacement of the original fluid by infiltration.

In FIG. 4, fibers or elongated particles 12 form the tightly packed bodies B, and homogeneously arranged and optionally tightly packed particles A in interparticle substance fill the voids between the tightly packed bodies B. In this case, the tight packing of the bodies B is the tight packing. obtained by simple mixing and casting, where the maximum fiber charge is limited only by the mixing and molding process. In this case, the interparticle substance may also be a substance which differs from the liquid by which the particles are arranged, the present interparticle substance being a substance introduced by replacement of the original fluid by infiltration.

In FIG. 5 shows the tightly packed fibers or elongated bodies 12 a dense package of bodies B arranged in a highly effective manner for establishing tight packaging of non-compressible fibers: parallel placement of the elongated bodies or fibers with homogeneously arranged and possibly tightly packed particles A in the space between the tightly packed bodies B. This structure is e.g. by filament winding 20 of the fibers 12 immersed in a slurry with homogeneously spaced and optionally tightly packed particles A. 5 is typical of the structure desired in ultra-high quality materials with high fiber charge and tensile and abrasion resistance, where the interparticle fluid between the particles A, e.g. are densely packed 25 microfine metal particles, by infiltration have been replaced by a strong interparticle substance, e.g. a metal or polymer.

In FIG. 6, Portland cement particles 16 form an open flocculent structure in an aqueous phase in the absence of surfactants.

FIG. Figure 7 shows how such a system will normally tend to sediment the cement particles when the flocculation tendency is eliminated by a superplasticizer.

FIG. 8 shows, on a further enlarged scale, a DSP paste system, e.g. a cement / ultrafine silica system with superplasticizer 93

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a portion wherein the voids between the cement particles 12 are filled with a suspension of ultrafine silica particles 18 which are substantially densely packed in the suspension. The number 20 denotes the interparticle substance which in this case e.g. is superplasticizer solution. In such a system, the tendency for sedimentation of the particles is minimized as a result of the extremely slow water flow around the ultrafine particles in accordance with classical hydrodynamics.

FIG. 9 shows a fine reinforcing fiber 22 embedded in a DSP matrix 10, e.g. a cement-based DSP matrix. By using such a cement-based DSP matrix instead of ordinary cement paste, the mechanical anchoring of the reinforcement increases even more than the strength, this increase being of one or several orders of magnitude. This is because the dimensions of the "roughness" or "wave configuration" of the fiber needed to achieve "mechanical locking" of the fiber in the matrix are reduced by one to two orders of magnitude, which also means that in the DSP matrix it is possible to achieve mechanical locking of fibers having a one to two orders of magnitude smaller diameter than the smallest fibers which can be mechanically locked in ordinary cement paste.

FIG. 10 illustrates the astonishing inner connection of the fresh 20 liquid to plastic cement-based DSP mortar 24 mounted on a supporting glass plate 26 under vibration (50 Hz - 10 s) and then held under flowing tap water (flow rate about 4 liters per minute). ). In this experiment, the mortar is typically kept under the flowing water for periods of 2 - 30 minutes without any visible washout of the mortar's components. The mortar is prepared as described in Example 9 International Patent Application no.

PCT / DK79 / 00,047th

FIG. 11 shows the repair of a bridge structure 28 in flowing water 30 (one stream) by underwater injection. Erosion cavities 40 had exposed 30 wooden piles 32 between a bottom structure 34 of ordinary concrete 36 and a foundation 38, thereby creating a danger of severe damage to the piles. Light-flowing cement-based DSP paste 24 was pumped through one of the drilled holes 42 into the cavity 40. As a result of its higher density, the DSP paste displaced water from the cavity 40 and increased into the remaining holes 42, thereby filling the cavity 94 completely.

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and the holes and formed a new cover layer, also on top of the foundation.

All casting was carried out under water and the creek flowed over the freshly cast DSP concrete, which, however, had such a high degree of internal consistency that essentially no washout took place.

FIG. 12 shows the repair of a wall element 44 of an underwater tunnel under a bay. A light-flowing DSP material 24 was filled into the cavity to be repaired. The cavity had a complicated shape and was heavily reinforced with steel reinforcement 46. The DSP material was introduced from one side through a hose 50 and rose at the other side of an existing concrete wall 36, filling the cavity between the concrete wall and formwork 48.

FIG. Figure 13 shows the casting of a high abrasion resistance lining within a steel tube 52 used for transporting powder (coal). A plastic tube 54 filled with sand 56 was placed in the interior of the tube and held in place by stiffening supports 58. A steel fiber reinforced DSP material 24 based on Portland cement and refractory bauxite was poured into tube 52 under slight external vibration and filled. completely the space between the steel tube 52 and the inserted plastic tube 54.

After curing of the DSP material, the sand was removed and the plastic tube 20 was pulled out.

FIG. 14 is a stress / strain diagram drawn during pressure testing of cylinders 10 cm in diameter and 20 cm high made of ordinary high quality concrete and DSP mortar with sand consisting of up to 4 mm refractory bauxite, respectively. The DSP material was DENSIT®-S from Aalborg Portland, Aalborg, Denmark. The measured compressive strengths were 72 and 270 MPa, respectively.

FIG. 15, FIG. 16 and FIG. 17 shows the compression of DSP concrete or mortar in a container 62 where an excess of liquid DSP paste 68 is pressed out of the pulp and flows past aggregates 64 and the opening between a piston 66 and the wall of the container 62 as the piston moves downward. This (Fig. 16) compresses the aggregate skeleton. After compression, the excess paste is removed (still under piston load). Then the plunger is removed and the aggregate skeleton expands slightly (elastic recoil), thereby pulling paste 68 a "V".

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slightly into the voids (suction), thereby forming inwardly curved paste / gas interfaces which, as a result of surface forces, stabilize the compressed drained material.

FIG. 18 shows the rolling of a plastic DSP material 68 by means of a pair of rolls 70 of an elastic material with a spacer 72 interposed between the rollers to form a semi-finished sheet or sheet of the DSP material which can be further molded .

FIG. 19.and FIG. 20 shows the formation of such a semi-manufactured sheet or sheet 74 between the two halves 76 of a printing mold (which itself can be made of a DSP material) to form a pipe section 80.

FIG. Figure 21 shows no extruder of a DSP material. From an extrusion mold 82, an extruded strand 84 of the DSP material passes a support 86, wherein electrical components 88, e.g. resistance components, are inserted into the V-shaped extruded band. The strip is cut off by means of a cutter 90 and the resulting sections 92 are then compressed into a mold 76 to form DSP-encapsulated components 94.

FIG. 22 shows pressure forming with DSP material 68 between a lower or an upper mold element 96 and 98, respectively; and FIG. 23 shows the molding of a large kitchen table / wash element of DSP material 68 in a large mold 100, 102.

FIG. 24 shows the manufacture of a reinforced DSP plate element by pressing freshly rolled sheets 110 and 112 of cement-based DSP on each side of a steel reinforcing grate 108 in a press 104, 106.

FIG. 25 shows the manufacture of a sandwich element of fiber reinforced DSP material, the fiber orientation of the upper component 110 being perpendicular to the fiber orientation of the lower component 112.

FIG. 26 and FIG. 27 shows the embedding of sanitary pipes 114 or heating pipes 116 in DSP construction elements.

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In FIG. 28, a freshly rolled sheet of cement-based DSP material for brick or tile 120 is cut using a grate-like insert.

FIG. 29 shows the barrier effect that occurs when a large body or large particle 221 close to the wall 223 inhibits small particles 185 from penetrating a narrow space between the large particle of diameter D and the wall. The size of space not available for the particles 18 is denoted f.

FIG. 30 shows the wall effect, showing particles 258 near a wall 256. The particle concentration is lower in the narrow space near the wall 10 than in the main mass. The thickness of the narrow space near the wall is approx. 1 particle diameter.

FIG. 31 shows the sedimentation of rod-shaped particles 248 in a liquid 250. Sedimentation from a liquid having a low particle or fiber concentration in the absence of surface forces results in a fairly dense package as the fibers turn freely to horizontal position without colliding with submersible neighboring particles.

Claims (69)

97 DK 163298 B A shaped object, characterized in that it comprises a continuous matrix, which matrix comprises Molded article according to claim 1, characterized in that the particles C are tightly packed, the dense packing being essentially a packing similar to that obtainable by gentle mechanical action of a system of geometrically equivalent shaped large particles where locking surface forces have no significant effect. A molded article according to claim 1 or 2.5, characterized in that the particles A are tightly packed or that the coherent structure A is formed from such tightly packed particles. Molded article according to any one of the preceding claims, characterized in that it contains additional bodies having at least one dimension which is at least one order of magnitude larger than the particles A, these additional bodies being bodies of a solid. , a gas or a liquid. D) additional bodies having at least one dimension at least one order of magnitude larger than Particles A, and mechanically mixing Particles A, water and concrete superplasticizer with Particles B and C and optionally additional Particles D until obtained a plastic mass viscose, and then, if necessary or desired, combines the resulting mass with particles and / or bodies of the above type (B, C, D) by mechanical means to achieve the desired distribution of the components, and to Finally, the resulting mass in the desired form casts in a low voltage region, optionally with incorporation, below the molding, of particles C and / or additional bodies D. Calculated on the total weight of particles A + B, where the amount of particles B corresponds substantially to tight packing thereof in the composite material with homogeneously packed particles A in the space between particles B, the amount of water substantially corresponds to the amount required to fill the space between particles A and B and the amount of concrete superplasticizer is sufficient to give the composite material a liquid to plastic consistency in a low stress range of less than 5 kg / cm 2, preferably less than 100 g. and C) compact shaped solid particles of a material having a strength greater than the strength of ordinary sand and stone used for ordinary concrete, typically a strength corresponding to at least one of the following criteria: 1. a piston press above 30 MPa at a packing rate of 0.70, over 50 MPa at a packing rate of 0.75 and above 90 B) solid particles of the order of 0.5-100 μτα, which particles are at least one order of magnitude larger than the corresponding particles mentioned under A), with at least 20% by weight of the particles being Portland cement particles and the amount of particles A is 5-50% by volume of the total volume of particles A + B, C) compact shaped solid particles of a material with a strength exceeding the strength of ordinary sand and stone used for ordinary concrete, typically a strength corresponding to at least one of the following criteria: 1) a piston pressure exceeding 30 MPa at a packing rate of 0.70, above 50 MPa at a packing rate of 0.75 and above 90 MPa at a packing rate of 0.80, determined by the method described herein (on particles of a material having a size ratio of the largest to the smallest particle substantially not exceeding 4), 2. a compressive strength of a composite material in which the particles are enclosed to 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 the case that substantially all particles are less than 4 mm), determined by the method described herein, 3. a Moh hardness (for the mineral comprising the particles) exceeding 7, and 4. a Knoop indentor hardness (for the mineral comprising the particles 30) exceeding 800, 104 DK 163298 B having these particles having a size of 100 μιη-0.1 m, water in a weight ratio of water to particles A + B of 0.12-0.30, and a concrete superplasticizer, the amount of super-plasticizer solid being in the range 1-4%, based on the total weight of particles A + B, the amount of particles B being substantially equal to tight packing thereof in the composite material with homogeneously packed particles A in the space between particles B, the amount of water substantially corresponding to 10 to the men The amount of concrete required to fill the space between particles A and B and the amount of concrete superplasticizer is sufficient to impart a liquid to plastic consistency to the composite material in a low stress range of less than 5 kg / cm 2, preferably less than 100 g. / cm 2, and optionally D) additional bodies having at least one dimension at least one order of magnitude larger than particles A. Molded article according to claim 4, characterized in that the additional bodies are selected from the group consisting of compact shaped bodies, plate-shaped bodies and elongated bodies. 5 A) homogeneously arranged inorganic solid SiO2-rich particles of size from ca. 50 Å to approx. 0.5 µτα, or a coherent structure formed from such homogeneously arranged particles, and B) tightly packed solid particles of the order of 0.5-100 µm and at least one order of magnitude larger than the respective particles. mentioned in A), or a coherent structure formed from such tightly packed particles, at least 20% by weight of the particles being Portland cement particles, the particles A or the coherent structure formed therefrom being homogeneously distributed in the space between the particles B wherein the particles A are present in an amount that is 5-50% by volume of the total volume of the particles A + B, 20 and the dense gasket is essentially a gasket similar to that obtainable by gentle mechanical action of a system of geometrically similarly shaped large particles in which locking surface forces have no significant effect, a concrete superplasticizer, id an amount of superplasticizer solids is in the range of 1-4%, based on the total weight of the particles A + B, which further comprises shaped embedded in the matrix 98 DK 163298 BC) compact shaped solid particles of a material having a strength which exceeds the strength of ordinary sand and stone used for ordinary concrete, typically a strength corresponding to at least one of the following criteria: 5 1) a piston pressure exceeding 30 MPa at a packing rate of 0.70, above 50 MPa at a packing degree of 0.75 and above 90 MPa at a packing rate of 0.80, determined by the method described herein (on particles of a material having a size ratio of the largest to the smallest particle substantially not exceeding 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 is greater than 4 mm) and 20 0 MPa (in the case of substantially all particles being less than 4 mm), determined by the method described herein, 3. a Moh hardness (for the mineral of the particles) exceeding 7, and 20 4) a Knoop indentor hardness (for the mineral made up of the particles) exceeding 800, said particles having a size of 100 / tm-0.1 m, and optionally D) additional bodies having at least one dimension, there is at least one order of magnitude larger than the particles A, the shaped article having been prepared using a weight ratio of water to the particles A + B of 0.12-0.30. Molded article according to claim 4 or 5, characterized in that the additional bodies are selected from the group consisting of metal rods, including steel rods, fibers, including metal fibers such as steel fibers, plastic fibers, Kevlar fibers, glass fibers, asbestos fibers, cellulose fibers, mineral fibers, high temperature fibers, whiskers, including inorganic non-metallic whiskers such as graphite and AI2O3 whiskers and metallic whiskers such as iron whiskers, heavy components, and hydrogen-rich components. Molded article according to any one of claims 4-6, characterized in that the additional bodies D are tightly packed. Molded article according to any one of the preceding claims, characterized in that the particles A show a substantially lower reactivity than the particles B, or substantially no reactivity. 100 DK 163298 B Molded article according to any one of the preceding claims, characterized in that the particles B comprise at least 50% by weight of Portland cement particles. Molded article according to claims 9, 5, characterized in that the particles B comprise particles selected from fine sand, fly ash and fine lime. Molded article according to any one of the preceding claims, characterized in that the particles A are silica dust particles 10 with a specific surface area of approx. 50,000-2,000,000 cm 2 / g. especially approx. 250,000 cm 2 / g. Molded article according to claim 11, characterized in that the silica dust particles are present in a volume that is 10-30 volume percent of the total volume of the 15 particles A + B. Molded article according to any one of the preceding claims, characterized in that the particles C consist of materials containing strong natural minerals, strong artificial minerals 20 or strong metals or alloys, the strength of the particles meeting at least one of the following criteria: 1 a piston pressure exceeding 30 MPa at a packing degree of 0.70, above 50 MPa at a packing degree of 0.75, and above 90 MPa at a packing degree of 0.80, preferably above 45 MPa at a packing degree of 0.70, over 70 MPa at a gasket size of 0.75 and above 120 MPa at a degree of packing of 0.80, determined by the method described herein (on particles of a material having a size ratio between the largest and smallest particle substantially not exceeding 4), 2. a compressive strength for a composite material in which 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 the case of substantially all particles). is less than 4 mm), preferably exceeding 200 MPa (in the case that a substantial amount of the particles is greater than 4 mm) and 220 MPa (in the event that substantially all the particles are less than 4 mm), determined by the method described herein, 3. a Moh hardness (for the mineral made up of the particles) exceeding 7, preferably exceeding 8, and 4. a Knoop indentor hardness (for the mineral comprising the particles 10 ), there exceeds 800, preferably exceeds 1500. Molded article according to claim 13, characterized in that the particles C consist of one or more of the following components: topaz, lawsonite, diamond, corundum, phenacite, spinel, beryl, chrysobearyl, tourmaline, andalusite, staurolite, zircon, boron carbide, tungsten carbide. Molded article according to claim 14, characterized in that the particles C consist of refractory bauxite. Molded article according to any one of the preceding claims, characterized in that the particles C are present in a volume, that is approx. 10-90% by volume, preferably 30-80% by volume, and especially 50-70% by volume, of the total volume of particles A, B and C. Molded article according to any one of the preceding claims, characterized in that it contains fibers as additional bodies D. Molded article according to claim 17, 30, characterized in that the fibers are selected from the group consisting of metal fibers, including steel fibers, mineral fibers, glass fibers, asbestos fibers, high temperature fibers, carbon fibers and organic fibers, including plastic fibers. Molded article according to claim 18, characterized in that the fibers are chopped fibers or 5 continuous fibers or yarns or ropes, or yarns or staple fibers, or fiber nets or webs. 20 MPa at a packing rate of 0.80, determined by the method described herein (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 170 MPa (in the case that a substantial amount of the particles is greater than 4 mm) and 200 MPa (in the case · substantially all particles are less than 4 mm), determined by the method described herein, 3. a Moh hardness (for the mineral made up of the particles) exceeding 7, and 4. a Knoop indentor hardness (for the mineral comprising the particles) exceeding 800, 5 having these particles. size of 100 μπι-0.1 m, and optionally D) additional bodies having at least one dimension that is at least one order of magnitude larger than the particles A, the shaped article having been prepared using a weight ratio of water to the particles A + B of 0.12-0.30, further comprising one or more surface layers having a substantially uniform thickness and a structure different from the above-defined structure adjacent to the surface layer (s) . It is capable of wetting the inner surface of the structure constituted by particles A and B, containing molecules of size at least one order of magnitude smaller than particles A, upon solidification, by cooling or polymerization leaving it a solid having substantially the same volume as the liquid, and subsequently solidifying the liquid by cooling or polymerization. 113 DK 163298 B 20 MPa at a packing rate of 0.80, determined by the method described herein (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 170 MPa (in case a substantial amount of the particles is greater than 4 mm) and 200 MPa (in the case of substantially all particles being less than 4 mm), as determined by the method described herein, 3) a Moh hardness (for the mineral made up of the particles) exceeding 7, and DK 163298 B uo 4. a Knoop indentor hardness (for the mineral comprising the particles) exceeding 800, these particles having a size of 100 μιη-0.1 m, and optionally A) inorganic SiO2-rich particles of a size of approx. 50 Å to approx. 0.5 µιη, B) solid particles of the order of 0.5 - 100 µα, which particles are at least one order of magnitude larger than the corresponding particles mentioned under A), with at least 20% by weight of the particles being Portland. cement particles, and the amount of Particles A being 5-50% by volume of the total volume of Particles A + B, 105 compact 164098 BC) compact shaped solid particles of a material with a strength exceeding the strength of ordinary sand and rock, used for ordinary concrete, typically a strength corresponding to at least one of the following criteria: 5 · 1) a piston pressure exceeding 30 MPa at a packing rate of 0.70, above 50 MPa at a packing rate of 0.75 and above 90 MPa at a degree of packing of 0.80, determined by the method described herein (on particles of a material having a size ratio of the largest to the smallest particle substantially not exceeding 4), 2. a compressive strength of a composite material le, 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 the case that substantially all particles are less than 4 mm) ), determined by the method described herein, 3. a Moh hardness (for the mineral made up of particles) exceeding 7, and 4. a Knoop indentor hardness (for the mineral made up of particles 20), exceeding 800, these particles having a size of 100 µm-0.1 m, and a concrete superplasticizer, the amount of super-plasticizer drying being in the range 1-4%, based on the total weight of the particles A + B, 25 wherein the amount of particles B substantially corresponds to tight packing thereof in the composite material with homogeneously packed particles A in the space between particles B, and the amount of concrete superplasticizer is sufficient to impart a liquid to the composite material. plastic consistency in a low voltage range of less than 5 30 kg / cm 2, preferably less than 100 g / cm 2, when a quantity of water is added which is substantially equal to the amount needed 106 DK 163298 B to fill the voids between particles A and B, this amount corresponding to a weight ratio of water to particles A + B of 0.12-0.30, and optionally D) additional bodies having at least one dimension that is at least one orders of magnitude larger than particles A. Molded article according to any one of the preceding claims, characterized in that it further contains reinforcing steel as rods or rods. Molded article according to claim 19 or 20, characterized in that the rods, rods or fibers are prestressed. Molded article according to claim 19 or 20, 15, characterized in that the additional bodies (fibers, rods or rods) have retained their geometric identity during the forming process. Molded article according to any one of the preceding claims, characterized in that this article is a sheet or sheet of thin-walled plane or corrugated form; A cord; a tube; a refractory lining or a component of refractory lining; a protective coating such as a protective coating applied to steel, ordinary concrete, masonry, sidewalks and roads; a roofing material such as a roofing sheet or roofing stone; an electrically insulating body; a shield against radioactive radiation; a deep seabed structure for use in deep water; a brake lining; a grinding unit; A container; an in situ cast oil well casing; or a supporting element in structures such as a beam, shell or column, typically as reinforced concrete, especially as prestressed concrete; a machine part; or a sculpture. Molded article according to claim 23, characterized in that its matrix is fiber-reinforced. 103 DK 163298 B B) tightly packed solid particles of the order of 0.5-100 µm and at least one order of magnitude larger than the respective particles mentioned under A), or a coherent structure formed from such tightly packed particles, at least 20% by weight of the particles are Portland cement particles, the particles A or the coherent structure formed therefrom being homogeneously distributed in the space between the particles B and the amount of the particles A being 5-50 volumes - percent of the total volume of particles A + B, 5 and the dense gasket being essentially a gasket similar to that obtainable by gentle mechanical action of a system of geometrically similarly shaped large particles where locking surface forces do not have any significant effect, a concrete superplasticizer, the amount of superplasticizer solid being in the range 1-4%, based on the total weight of the particles A + B, and further comprises, embedding in the matrix C) compact shaped solid particles of a material having a strength greater than the strength of ordinary sand and stone used for ordinary concrete, typically a strength corresponding to at least one of the following criteria: 1. a piston pressure exceeding 30 MPa at a packing rate of 0.70, above 50 MPa at a packing rate of 0.75 and above 90 A composite material for the manufacture of a shaped article containing, A) inorganic SiO 2 * rich particles of about size. 50 Å to approx. 0, 5 pm, 26. Composite material for the manufacture of a shaped article, containing material, Composite material according to claim 25 or 26, characterized in that the particles A are present in a volume substantially corresponding to tight packing, for filling the space between the particles B when tightly packed, and the surface surfactant dispersant is present in an amount sufficient to allow tight packing of the particles A in a low voltage range of less than 5 kg / cm 2, preferably less than 100 g / cm 2. Composite material according to any one of claims 25-27, 15, characterized in that the particles A are silica dust particles with a specific surface area of approx. 50,000 - 2,000,000 caP / g, especially approx. 250,000 cm 2 / g, and the particles B comprise at least 50% by weight of Portland cement. Composite material according to any one of claims 25-28, 20, characterized in that the particles C are present in a volume which corresponds substantially to a tight gasket between the particles C, the dense gasket being essentially a gasket. similar to that which can be obtained by gentle mechanical action of a system of geometrically similarly shaped large particles, in which locking surface forces have no significant effect. Composite material according to claim 28 or 29, characterized in that the particles B comprise particles selected from fine sand, fly ash, fine lime and fine refractory bauxite. Composite material according to any one of claims 28-30, 30 characterized in that the concrete superplasticizer is an alkali or alkaline earth metal salt of highly condensed naphthalene sulphonic acid / formaldehyde condensate, which typically consists of more than 70 percent molecules containing 7 or more naphthalene nuclei. Composite material according to claim 31, characterized in that the alkali or alkaline earth metal salt is a sodium or calcium salt. Composite material according to claim 31 or 32, characterized in that the amount of superplasticizer solids is in the range of 2 to 4%, based on the total weight of Portland cement and silica dust. Composite material according to any one of claims 31-33, characterized in that the weight ratio of water to Portland cement and any other particles B plus silica dust is from 0.12 to 0.20. Composite material according to any one of claims 25 to 34, 15, characterized in that the particles C consist of materials containing strong natural minerals, strong artificial minerals or strong metals or alloys, the strength of the particles meeting at least one of the following criteria: 1 a piston pressure exceeding 30 MPa at a degree of packing of 20 0.70, above 50 MPa at a degree of packing of 0.75 and above 90 MPa at a degree of packing of 0.80, preferably above 45 MPa at a degree of packing of 0, 70, above 70 MPa at a packing rate of 0.75 and above 120 MPa at a packing rate of 0.80, determined by the method described herein 25 (on particles of a material having a size ratio of the largest to the smallest a particle not substantially exceeding 4); 2. a compressive strength of a composite material wherein the particles are enclosed in a specific matrix exceeding 30 170 MPa (in the case of a substantial amount of the particles is greater than 4 mm) and 200 MPa (in the case that substantially all particles are less than 4 mm), preferably exceeding 200 MPa (in case a substantial amount of the particles is greater than 4 mm). mm) and 220 MPa (in case substantially all the particles are less than 4 mm), determined by the method described in this specification 5, 3. a Moh hardness (for the mineral of the particles) exceeding 7, preferably exceeds 8, and 4. a Knoop indentor hardness (for the mineral of the particles) exceeding 800, preferably exceeding 10 1500. Composite material according to claim 35, characterized in that the particles C consist of one or more of the following components: topaz, lawsonite, diamond, corundum, phenacite, spinel, beryl, chrysobearyl, tourmaline, andalusite, staurolite, zircon, boron carbide , tungsten carbide. Composite material according to claim 36, characterized in that the particles C consist of refractory bauxite. 38. A process for making a shaped article or a part of a shaped article, characterized by combining A) inorganic solid SiO2-rich particles with a size of from approx. 50 A to approx. 0.5 µm and B) solid particles of the order of 0.5 to 100 µτα which are at least one order of magnitude larger than the respective particles mentioned under A), with at least 20% by weight of the particles being Portland cement particles, and wherein the amount of Particles A is 5-50% by volume of the total volume of Particles A + B, water in a weight ratio of water to Particles A + B of 0.12-0.30, and a concrete superplasticizer, the amount of superplasticizer solids is in the range of 1-4%, The method according to claim 38, characterized in that the stress area responsible for forming the mass is mainly due to gravity forces acting on the mass, or inertia forces acting on the mass, or contact forces, or the simultaneous action of two or more. several of the above forces. Method according to claim 38, 25, characterized in that the voltage range which is mainly responsible for the formation of the mass is due to oscillating forces with a frequency of between 0.1 and 10 5 Hz, the oscillating forces being of the one of claim 39 or due to a combination of such oscillating forces with non-oscillating forces of the type of claim 39. 1U DK 163298 B Method according to claim 38, characterized in that the article or part of the article is formed by extrusion or rolling at a forming pressure of up to 100 kg / cm 2. A method according to claim 38, characterized in that the article or part of the article is formed by spraying, painting or brushing, injecting or applying a layer of the pulp to a surface and adapting the pulp to the surface shape. Method according to claim 38, characterized in that the article or part of the article is formed by centrifugal casting. Method according to claim 38, characterized in that the mass as a continuous mass 15 is poured into a liquid where it displaces part of the liquid and arranges itself as a continuous mass. The method according to claim 41, characterized in that the liquid is water and the mass is paste, mortar or concrete for building an underwater structure. 46. Molded articles made by the method of any one of claims 38-45. 47. Molded articles made from composite material according to any one of claims 26-37. The shaped article according to any one of claims 1-24 and 46-47, characterized in that at least part of the matrix contains an additional solid in the voids in the structure constituted by particles A and B. 112 DK 163298 B The molded article of claim 48, characterized in that the additional solid is selected from the group consisting of organic polymers such as polymethyl methacrylate or polystyrene, low melting metals and inorganic solid metalloids such as sulfur. Molded article according to claim 48 or 49, characterized in that at least that part of the matrix adjacent to the outer surfaces of the article contains the additional solid in the cavities of the structure constituted by particles A 10 and B. 51. A method of making a shaped article according to any of claims 48-50, characterized in that a shaped article according to any one of claims 1-24 and 46-47 is infiltrated in whole or in part with a liquid. after which the liquid is converted to solid. Method according to claim 51, characterized in that the infiltration is carried out with a liquid which exhibits at least one of the following properties: The method according to claim 51 or 52, characterized in that the efficiency of the liquid infiltration is increased by one or more of the following precautions: drying of the article or part thereof to be impregnated, applying vacuum to the article or part thereof, which must be impregnated prior to the infiltration treatment, applying external pressure to the infiltration fluid after contacting the object with the infiltration fluid. 54. Use of a composite material containing A) inorganic solid SiO2-rich particles of about size. 50. to approx. B) solid particles of the order of 0.5 to 100 μα, which are at least one order of magnitude larger than the 15 corresponding particles mentioned under A), with at least 20% by weight of the particles being Portland cement particles, and wherein the amount of particles A is 5-50% by volume of the total volume of particles A + B, C) compact-shaped solid particles of a material having a strength exceeding the strength of ordinary sand and rock used for ordinary concrete. typically a strength corresponding to at least one of the following criteria: 1 a piston pressure greater than 30 MPa at a packing rate of 0.70, above 50 MPa at a packing rate of 0.75 and above 90 25 MPa at a packing rate of 0.80; determined by the method described herein (on particles of a material having a size ratio of the largest to 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 is greater than 4 mm) and 200 MPa (in the case that substantially all particles are less than 4 mm), determined by the method described herein, 3. a Moh hardness (for the mineral comprising the particles) exceeding 7, and 4. a Knoop indentor hardness (for the mineral comprising the particles 10) exceeding 800, these particles having a size of 100 µm-0.1 meter water in a weight ratio of water to particles A + B of 0.12-0.30, and a concrete superplasticizer, the amount of super-plasticizer solid being in the range 1-4%, based on the total weight of particles A + B, the amount of particles B being substantially equal to tight packing thereof in the composite material with homogeneously packed particles A in the space between particles B, the amount of water substantially corresponding to 20 to the amount needed to fill the space between particles A and B and the amount of concrete superplasticizer is sufficient to impart a liquid to plastic consistency to the composite material in a low stress range of less than 5 kg / cm 2, preferably less than 100 g / cm 2, and optionally D) additional bodies having at least one dimension at least one order of magnitude larger than the particles A for the manufacture of shaped articles selected from the group consisting of in situ cast oil boreholes; kanaludfyldninger; crack fill 115 DK 163298 Bings; sheets, slabs and roof tiles of thin-walled or corrugated form; anti-corrosion protection coatings applied to steel and concrete bodies; wires; tube; electrical insulating bodies; shielding from radioactive radiation; seabed structures for deep water use; 5 brake pads; grinding aggregates; containers; machine parts; and sculptures. 55. A method of manufacturing a shaped article selected from the group consisting of in situ cast oil boreholes; kanaludfyldninger; revneudfyldninger; sheets, sheets and roof tiles of thin-walled plane 10 or corrugated form; anti-corrosion protection coatings applied to steel and concrete bodies; wires; tube; electrical insulating bodies; shielding from radioactive radiation; seabed structures for deep water use; brake linings; grinding aggregates; containers; Raa skin parts; and sculptures; characterized in combining A) inorganic solid SiO2-rich particles of about size. 50. to approx. B) solid particles of the order of 0.5 to 100 μη, which particles are at least one order of magnitude larger than the 20 corresponding particles mentioned in peaks A), with at least 20% by weight of the particles being Portland cement particles, and wherein the amount of particles A is 5-50% by volume of the total volume of particles A + B, C) compact shaped solid particles of a material having a strength exceeding the strength of ordinary sand and stone used for ordinary concrete. typically a strength corresponding to at least one of the 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 30 MPa at a packing rate of 0.80; determined by the method described herein (on particles of a material having a size ratio of the largest to the smallest particle substantially not exceeding 4), 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 the case that substantially all particles are less than 4 mm) determined by the method described herein, 3. a Moh hardness (for the mineral made up of the particles) exceeding 7, and 4. a Knoop indentor hardness (for the mineral made up of the particles 10) which exceeds 800, these particles having a size of 100 µun-0.1 m, water in a weight ratio of water to particles A + B of 0.12-0.30, and a concrete superplasticizer, the amount of super-plasticizer drying is in the range 1-4%, based on the total weight of particles A + B, where the amount of particles B corresponds substantially to tight packing thereof in the composite material with homogeneously packed particles A in the space between particles B, the amount of water in it essential equals 20 t in the amount needed to fill the space between particles A and B and the amount of concrete superplasticizer is sufficient to impart a liquid to plastic consistency to the composite material in a low stress area of less than 5 kg / cm 2, preferably less than 100 g / cm 2, and optionally D) additional bodies having at least one dimension that is at least one order of magnitude larger than particles A, mechanically mixing particles A, water and concrete superplasticizer with particles B and C and optionally additional bodies D until a viscous to plastic mass is obtained, and then, if necessary or desired, combines the resulting mass with particles and / or bodies of the above type (B, C, D ) by mechanical means to obtain the desired distribution of the components, and finally, the resulting mass in the desired mold casts in a low voltage region, possibly incorporating orering, during casting, of additional particles C and / or additional bodies D, A molded article according to claim 1, characterized in that the article has a compressive strength greater than 150 MPa, preferably above 180 MPa, measured on a test body having a diameter of 10 cm and a height of 20 cm when the largest of the compact shaped bodies are greater than 4 mm and 15 over 180 MPa, measured on a test body having a diameter of 3 cm and a height of 6 cm when the largest of the compact shaped bodies is at most 4 mm. 57. A molded article, characterized in that it comprises a coherent matrix, which matrix comprises A) homogeneously arranged inorganic solid SiO2-rich particles of a size of from ca. 50 Å to approx. 0.5 μια, or a coherent structure formed from such homogeneously arranged particles, An article according to claim 57, characterized in that the structure constituted by particles A, B, C and optionally D exhibits any of the features defined in any of claims 3-27. The article of claim 57 or 58, 20, characterized in that the material constituting a surface layer is selected from the group consisting of glass; ceramics; plastic; metals; tree; paper; leather; cement mortar; concrete; fiber reinforced cement materials. An article according to any one of claims 57-59, 25 characterized in that it is an electrically insulating component, a furniture, a bookshelf, a door, a safe or part thereof, a radioactive material container, a sculpture. , a supporting element such as a pillar, a wall, a floor or roof element, a ship's hull, a pipe or a pipe or a chimney. 1 '120 DK 163298 B A process for making an article according to any one of claims 57-60, characterized in that A) inorganic solid SiC> 2-rich particles having a size of 5 from about 5 are combined. 50 Å to approx. 0.5 µm and B) solid particles of the order of 0.5-100 µπι, which particles are at least one order of magnitude larger than the respective particles mentioned under A), with at least 20% by weight of the particles being Portland cement particles, and 10 wherein the amount of particles A is 5-50% by volume of the total volume of particles A + B, water in a weight ratio of water to particles A + B of 0.12-0.30, and a concrete superplasticizer, The plasticizer solids are in the range of 1-4%, based on the total weight of particles A + B, the amount of particles B being substantially equivalent to tight packing thereof in the composite material with homogeneously packed particles A in the space between particles B, the amount of water substantially 20 corresponds to the amount needed to fill the space between particles A and B and the amount of concrete superplasticizer is sufficient to give the composite material a sounding to plastic consistency in a low stress area of less than 5 kg / cm 2, preferably less than 100 g / cm 2, 25 and C) compact shaped solid particles of a material with a strength greater than ordinary sand strength. and stone used for ordinary concrete, typically a strength corresponding to at least one of the following criteria: 121 1. a piston pressure exceeding 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 rate of 0.80, determined by the method described herein (on particles of a material having a size ratio of the largest to the smallest particle substantially not exceeding 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 is greater than 4 mm) and 200 MPa (in the case of that essentially all particles are less than 4 mm), determined by the method described herein, 3. a Moh hardness (for the mineral made up of the particles) exceeding 7, and 15 4) a Knoop indentor hardness (for the mineral, the particles consists of) exceeding 800, these particles having a size of 100 μπι-0.1 m, and optionally D) additional bodies having at least one dimension 20 at least one order of magnitude larger than particles A, by mechanically mixing the particles A, the water and the concrete superplasticizer together with particles B and C and optionally additional particles D until a viscous to plastic mass is obtained, and then, if necessary or if desired, combining the resulting mass with particles and / or bodies of the aforementioned type (B, C, D) by mechanical means to achieve the desired distribution of the components, and finally, the resulting mass contacts one or more layers having a structure different from one another. raises the cured structure of the resulting mass, in a region of low tension, optionally with incorporation, during casting, of particles C and / or bodies D, and cures the molded mass in such a way that the layer or the layers are integrated with the cured mass so that it or they form one or more surface layers that cover the mass. Method according to claim 61, characterized in that the mass is molded in a space between two layers or in the interior of a hollow structure. 63. A method according to claim 61 or 62, 10, characterized in that the stress area responsible for forming the mass is mainly due to gravity forces acting on the mass, or inertia forces acting on the mass, or contact forces, or the simultaneous effect. of two or more of the above forces. 64. A method according to claim 61 or 62, characterized in that the voltage range mainly responsible for the formation of the mass is due to oscillating forces 20 having a frequency of between 0.1 and 10 5 Hz, the oscillating forces being claim 63 or is due to a combination of such oscillating forces with non-oscillating forces of the type mentioned in claim 63. A method according to claim 61 or 62, 25, characterized in that the article or part of the article is formed by extrusion or rolling at a forming pressure of up to 100 kg / cm 2. A method according to any one of claims 61-63, characterized in that the article or part of the article 30 is formed by injection. 123 DK 163298 B Method according to claim 61 or 62, characterized in that the article or part of the article is formed by centrifugal casting. A method according to claim 61 or 62, 5, characterized in that the mass is poured out as a continuous mass into a liquid, where it displaces part of the liquid and arranges itself as a continuous mass. 69. A method according to claim 68, characterized in that the liquid is water and the mass is paste, mortar or concrete for building an underwater structure.