DE2058274B2 - METHOD OF MANUFACTURING CURED CEMENT MATERIAL - Google Patents

Description

The invention relates to a method for producing hardened cement material.

With the rapid progress in modern construction there is a great need to improve Properties of various building materials emerged. Although hardened cement made from cement paste, Cement mortar, concrete or the like has an extremely high compressive strength, he has a Number of serious drawbacks e.g. B. extremely low tensile strength, flexural strength and Impact resistance, poor toughness, high brittleness, low abrasion resistance and Insufficient chemical resistance (to sea water, chemicals such as acids, alkalis etc.).

In order to improve the above-mentioned disadvantages of the hardened cement, a cement material containing organic polymers, called polymer cement mortar or polymer concrete, has already been put on the market, and intensive work is being carried out on improving this material.
It is known that, in comparison with more common cement mortars and concrete, the hardened materials of: type of polymer cement, such as polymer cement mortar and polymer concrete, have advantageous properties, e.g. B. considerably increased tensile strengths, flexural strengths, impact strengths and adhesive strengths, excellent chemical stability, excellent water repellency and an 'exceptionally low tendency to develop efflorescence (efflorescence are caused by alkaline substances in a hardened cement).

In contrast to ordinary cement mortar or concrete, which contain no aggregates and which are called »eir fan-shaped mortar "or" simple concrete "denotes these hardened materials ai polymer cement have the disadvantage that they protrude specified mechanical strength properties are characteristic of polymer cements develop only when cured in the atmosphere

3 4

If they are cured moist, in particular with acrylamide and formaldehyde to form a cement for water or steam, the mechanical rapid curing is added. As further Kom strengths "even worse than that of simple components of the reaction mixture are sodium mortar and simple concrete, since the hydration hydroxide and a redox catalyst called The and hardening of the cement as a result of the water 5 properties of the absorption process known according to this However, the swelling and decomposition of the polymer mortar obtained are still not prevented by polymerizate during wet curing; this applies in particular to steam curing. which is unavoidable according to the method known from JA-AS 4215/1969 concrete casting during construction, 10 can be obtained, for example, if the concrete is poured under water and not enough; this known method exists and has to be hardened So the material for practical is that you can use sodium acrylate or cement Sodium purposes unsuitable, since although the construction as a result of methacrylate, a water-soluble vinyl monomer and early removal of the cladding accelerates a water-soluble divinyl compound as well as a, but the long-term strength of the obtained Ze- i ₅ redox catalyst admits.

Mentbauwerkes is worse than when using the The object of the invention is the

plain mortar or plain concrete. Usefulness of the usual hardened material

In the manufacture of molded articles from polymer-cement-type lines to expand, such as Cement, the hardening with steam is an indispensable thing- that the properties of these materials of the Ausbaren step, since the poured cement in as possible 20 hardening conditions are independent that the chakurzer Time to maximum strength with characteristic mechanical strength properties hardened, taken out of the casing and fully developed and that at the same time the mass dispatched must be so that the cladding is not only stable when hardening in the Atmomögüchst can often be used and the sphere, but also when hardening in water or Productivity can be increased. 25 steam can be improved as it does when hardening

The use of such polymer cement masses of an ordinary cement mortar or concrete of was practically impossible in this case as the shape is case.

pieces when removing the casing odei on the This object is according to the invention by a

Transport broke because the short-term solidification in the process of producing hardened cement hardening dissolved with steam, compared with simple material, in which cement, water, a water-based mortar or simple concrete, although soluble ethylenically unsaturated monomer, was poor the deformability of the cement was better and the more water-soluble monomer, water-soluble Molded articles had more precise dimensions. inorganic alkali metal compound and a redox

Another disadvantage of the usual cured catalyst system used is the VerMaterials made of polymer cement, which is too difficult to drive, is characterized by the fact that one The poor dimensional stability, especially the base material made of cement, possibly with special features Beat the strong shrinkage during hardening, water to make the cementine the atmosphere and with steam, whereby Schwan materials and (a) 2 to 30 wt .-% (based on the changes in the shape and dimensions of the form water) of the ethylenically unsaturated monomer Objects preserved and cracks in the structure created 40 and (b) 0.02 to 20% by weight (based on the water) will. further monomers with a catalytic

Despite the essentially good properties of the amount of redox catalyst system in the presence hardened material made of polymer cement (me- a water-soluble inorganic alkali metal mechanism Properties and improvement of the compound from the group of oxides, hydroxides, workability), is the actual usefulness of these 45 sulfates, metasulfites, pyrosulfates, carbonates, chro-materials limited to very narrow areas where a mate, bichromate, aluminate, tungstate, stannate, Curing in the atmosphere under suitable orthophosphates, tripolyphosphates, manganates, phosphate-temperature and humidity conditions possible phormolybdate, phosphotungstate and / or aluist and where there is a need for good dimensional accuracy, do not use minium alum and / or in the presence of potassium special arrives. 50 chrome alum hardens in water or steam, whereby

GB-PS 10 65 053 relates to a process for producing these alkali metal compounds in the case of cementitious compositions, in which oxides and hydroxides in amounts of 0.5 to at least one polymerizable unsaturated 10% by weight and otherwise in amounts from 2 to polyester with at least one used with the polyester 40% by weight, based on the amount of water used for the compatible polymerisable, ethylenically un- 55 make,
saturated monomers in the presence of hydraulic It has been found that when using this cement and a polymerization initiator mixing process, the construction time can be shortened because the polymerizes. With this known method, casings cannot be removed soon after the cement has been poured, and no water-soluble, ethylenically unsaturated monomaterial can be removed and the molders are used, the cement being used as a filler in the manufacture of Hume pipes. DT-OS 14 71 481 relates, among other things, to the addition of differently shaped blocks and pre-tensioned water-soluble sulphate as binding retardation concrete blocks in the form can be improved, medium when setting cement in a mixture with since the separation of water and aggregates in acrylic or Methacrylic acid salts. However, according to these methods, which are known to mortar and concrete in centrifugal casting and vibration casting, none can be satisfied and is suppressed in the case of compression deformation. It would achieve the flexural strengths and compressive strengths. also found that by using this FR-PS 15 02 675 relates to a method in the process, the workability of a cement mortar, an aqueous solution of a reaction product made from or a concrete when sprayed on, can be improved

5 6

so that sliding down or falling down can reduce seeds, either alone or in a mixture of two

can be prevented; also spring water and seepage or multiple compounds can be used. U.N

water can be obtained by spraying on this cement material. The water-soluble, ethylenically unsaturated monota)

be contained. According to the invention, mers are generally used in amounts of

The excellent properties of the thus obtained 5 common 2 to 30%, preferably about 2.5 to _W (hardened material of a polymer-alkali 6.0% by weight, based on the compound-cement cement are neither due to the formation one of the cement paste, mortar or concrete use simple composite material made from the organic quantity of water used.When using polymers and the hardened cement hydrate less than 2% of the monomer, no noticeable _e i (as is the case with the usual hardened material io effect, while if more than 30% ο polymer cement is used) the effect is not significantly improved by a simple one, which is why a combination of an inorganic compound is uneconomical. d of an alkali metal and hardened cement hydrate The crosslinking monomer is usually conditional (cf. the examples below); these amounts of 0.02 to 20% by weight, preferably of _e Properties are rather used by the synergetic 15 about 0.1 to 10 wt .-%, based on the amount of water used to effect the three-fold combination of organic making of the cement paste, the mortar or the BePolymer, inorganic compound of an alkali clay. With metal and hardened cement hydrate to a limited extent. use of less than 0.02% of this monomer

The cured zeolite produced according to the invention is insufficient in crosslinking, while at

ment material not only has better properties than 20 use more than 20% the effect is not

the usually hardened material, is significantly improved by the poly or in some cases j

mer cement type in the field of application in which the reduction in strength also occurs. j

the latter is used in practice, but also shows. As a redox catalyst system can fiction |

excellent properties, such as mechanical strength- according to all known combinations used s

dimensions, dimensional accuracy and workability on request. Potassium persulfate or ammonium persulfate f

Areas of application in which this is usually suitable as an oxidizing component. Examples

cured cement-polymer material its mecha- for suitable reducing components are tri- |

niche strengths and its other properties ethylenetetramine, hexamethylenediamine, dimethylami-

not fully developed, as in the field of nopropanol, nitrilotrispropionamide, / ff-dimithylami-

Wet curing, e.g. B. with water or steam or 3 ° noethanol, yS-dimethylaminopropionitrile, 0-diketones,

in areas of application where a good measure of sodium formaldehyde sulfoxylate, etc.

durability is required. These catalysts are in catalytic! Men-

According to the invention, for example, in the Hergen, generally in amounts of 1 to 30% by weight,

position of molded objects, compared with based on the polymerizable components,

homely mortar or concrete, not only the used, whereby the amount of the respective com-

the workability of the material is improved, but it is a combination of oxidizing and reducing components

normal strength develops faster, so that nente depends.

The curing time with steam, which is necessary for the formation of the water-soluble, inorganic compounds of sufficient strength to detach the alkali metals, which are used according to the invention and for transporting the molded article 40, are, for example, alkali oxides and hydroxides, can be reduced whereby the aluminates, carbonates, -stanate, orthophosphates, Cladding and the molding machine tripolyphosphates often comparable, chromates, -bichromate can be -wolfwendet so that the ^D roduktivität ER ramate, sulfates, -methasulfite , -pyrosulfate, -manhöhen. ganates, -phosphomolybdates, -phosphotungstates, -alu-

As water-soluble ethylenically unsaturated mono- 45minium alum etc.

According to the invention, mers can, for example, acrylic compounds. Particularly effective compounds are the car-

amide, N-methylolacrylamide, methacrylamide, N-me- bonate, chromate, bichromate, tungstate, sulfate,

ethylene methacrylamide, acrylonitrile, hydroxymethyl meth and aluminum potassium sulfate, chromium (3) potassium

acrylate, methacrylic acid and their metal salts, acrylic sulfate, especially sodium sulfate, sodium carbonate,

acid and its metal salts, etc. can be used. 50 potassium sulfate, sodium dichromate, sodium tungstate

Of these monomers, particularly preferred are etc.

Acrylamide or a mixture of acrylamide as these water-soluble inorganic alkali compounds

The main component and a small amount of fertilizer are expediently in amounts of about 0.5 j

Sodium acrylate and / or sodium methacrylate up to 10% by weight (oxides or hydroxides) or about;

turns. 55 2 to 40% by weight (other alkali compounds), be |

As water-soluble, crosslinking monomers, the amount of the cement i

for example methylenebisacrylamide, 1,3-di- (acrylic paste, the water used in the mortar or concrete \

amidomethyl) - 2 - imidazolidone, 1,3 - di - (methacrylic) used. These alkali compounds do not show any

amidomethyl) -2-imidazolidon, Hexahydrotriacryloyl- noticeable effect when used in amounts outside ■

triazine and unsaturated amides, the dimethylene ether- 60 of the specified ranges are used. ;

contain bonds, such as diacrylamide dimethyl ether, The invention can be incorporated in various ways

Dimethacrylamiddimethyläthei etc. can be used in practice; for example the

the. Of these compounds, 1,3-di- (acrylic- embodiment given below) are good results.

amidomethyl) -2-imidazoliden, 1,3 - di - (methacrylic- results:

amidomethyl) -2-imidazolidon and Mcthylenbisacryl- 65 Das for making the cement paste, the mortar

amide used with particular preference. or the water used in the concrete is divided into two parts

Each of the above-mentioned ethylenically subdivided, one of which is used to produce the main

(Tcsaturated monomers and crosslinking mono-

saturated monomer, the crosslinking monomer and the reducing component of the redox catalyst is networked; the other part is used to make cinci initiator solution for curing, which is the oxidizing component of the redox catalyst system and contains the inorganic alkali compound. These two previously made Solutions are mixed together at the time of mixing and the cement paste, the mortar or added to concrete.

The time for the polymerization of the monomers to start, i.e. H. the hardening time of the cement paste, the mortar or the concrete can be achieved by suitable selection of the combination of the redox catalyst components and regulated by their quantities.

The invention is illustrated below by way of examples explained, in which all parts and percentages are by weight. The one in the examples The sand and gravel used has the particle size distribution given in Table A, and the used Cement was an ordinary Portland cement with the composition given in Table B.

Table A.

Particle size distribution of sand and gravel

Particle size

Sand (fine aggregates)

0.074-0.1 mm
0.1-0.2 mm
0.2-0.3 mm
0.3-0.4 mm
0.4-0.5 mm

Gravel (coarse aggregates)

1-5 mm

5 - 10 mm

10-20 mm

20-25 mm

Weight%

6th
69

23
1
1

46

43

Table B.

Composition of the cement

Components example 1 Wt% Loss on ignition 0.4 Insoluble components 0.4 SiO _a 22.1 Al ₂ O ₃ 5.2 Fe ₂ O ₃ 2.9 CaO 65.3 MgO 1.3 SO ₃ 1.7

To test the strength according to the method JIS R-5201-1964 (JIS = Japan Industrial Standard) was each of the mortar samples with the ingredients specified in Table 1 placed in a steel mold (a Triple mold for the production of three square bars with the dimensions 4.0 χ 4.0 χ 16.0 cm). After 2 hours, each mortar-containing form was placed in a steam curing chamber with a temperature brought from 65 ° C. After a curing time of

The mold was removed from the curing chamber for 5 hours, whereupon the cured sample was immediately removed from the mold. The compressive strength of the samples was determined immediately after Removal from the mold and after 6 weeks using a dynamometer-type testing device measured with a hydraulic pendulum. During the

6 weeks after removal from the mold, the samples were left in the atmosphere; H. in a Chamber cured at a temperature of 20 ° C and a humidity of 65%. The results of the sand strength tests are given in Table 2.

Table 1

Composition of the mortar

Hardened material cement, sand, mixing water, parts

Ordinary mortar 100 300 water 40 Polymer mortar 100 300 Main solution:
Acrylamide 0.10 Sodium methacrylate 0.10 Sodium acrylate 0.10 Methylene-bis-acrylamide 0.15 / 3-dimethylamino 0.20 propionitrile water 18.35 Initiator solution: Potassium persulfate 0.20 water 19.80

Mortar with polymer and more inorganic component

100

Mortar with an- 100

organic compound

300

300

The two solutions were mixed together and used to mix the mortar

There were two solutions with the same composition as the Above main solution and initiator solution prepared 5 parts of the inorganic compound were dissolved in the initiator solution. A mixture of the two solutions was used to mix the mortar

5 parts of the inorganic compound were in 40 parts of water dissolved and the solution was used to make the mortar

Table 2

Influence of the addition of various inorganic compounds

Inorganic
link

(A) Compressive strength of the mortar with inorganic compound, kg / cm "

right away
after this
Harden
with steam

:after

6 weeks

(B) compressive strength
of the mortar with polymer
and inorganic compound, kg / cm "
immediately after
after 6 weeks
Harden
with steam

(B)

right away
after this
Harden
with steam

(A)

after

6 weeks

Remarks

NaHSO ₁
Na ₂ CO ₃
NaAlO ₂
K ₂ [Sn (OH) ₆ ]
Na ₃ PO ₄ • 12 H ₂ O
Mg (NO ₃ I ₂ · 6H ₂ O

101
70
45
75
47
37

256 159 103 164 156 206

139 128 93 88 53 10

340 280 266 267 260 203 1.38
1.88
2.06
1.17
1.13
0.27

1.33
1.76
2.53
1.63
1.67
1.01

Invent
manure

comparison

Note- The strength of the simple mortar without the addition of inorganic compounds and polymers, as well as those of polymer mortars containing polymer only are given in the table below.

Plain mortar
Polymer mortar

After 6 weeks kg / cm ² with steam kg / cm *

86
10

254 210

From the test results given in Table 2, it can be seen that the with a combination A mortar mixed with a polymer and an inorganic compound of an alkali metal is essentially one Has higher strength than the simple mortar without additives, the polymer mortar, which only contains the polymer contains, and the mortar mixed with the inorganic compound alone. You can also see that do not see the strength using a combination of the polymer and a magnesium compound improved.

From the values in the table it is clear that the improvement in strength on the synergetic Effect of the combination of polymer and inorganic compound is based.

Example 2

According to the strength method JIS R-5201-1964, a cement material composed of 100 parts of cement and 300 parts of sand was mixed with a water-soluble ethylenically unsaturated monomer, a water-soluble crosslinking monomer, a redox catalyst and 5 parts of an inorganic compound together with water, the in Table 3 indicated proportions were used. The mixture was molded in the same shape as in Example 1. After 2 hours, the mold containing the mortar was placed in a steam curing chamber at 65 ° C. After a hardening time of 4 hours, the hardened mortar was released from the mold, a hardened cement material (cement mortar) being obtained. The flexural strength and the compressive strength were measured R-5201-1967 according to the method JIS immediately after the peeling of the mold and after a 4-week storage in the atmosphere at 20 ⁰ C and 65% humidity. The change in length of the sample was also determined according to the JIS A-1124-1957 method. The following definition applies:

Change in length (%) =

(Length of the hardened material _n ~ "", τ-..
n «rh 4 weeks curing - (length of the mold)

after 4 weeks of curing)

The results obtained are shown in Table 3.

(Length of the shape)

100

Table 3

Type of cured
Materials

Shares

Water soluble water soluble

Ethylenic tinge- cross-linking

saturated monomer, monomer, parts

TeDe

Redox catalyst, parts

Inorganic compound

Water, parts

Plain mortar Polymer mortar Mortar with polymer and more inorganic link

Acrylamide 1.88

1,3-di- (acrylamidomethyl) -2-imidazolidone

^ -Dimethylammopropionitru 0.24 Potassium persulfate 0.36

Li ₂ SO ₄ · H ₂ O Li ₂ CrO ₄ · 2 H ₁ O Na ₂ CO ₈ K ₂ WO ₄ - ^ H ₂ O

AlCV 6 H ₂ O CuSO ₄

Mg (NOa) ₂ -OH ₂ O Ba (OH) ₈ «8 H ₂ O

Continuation of table 3

Type of cured
Materials

Strength immediately after releasing the form

Firmness after 4 weeks

Change in length

Flexural strength
kg / cm ¹

Compressive strength kg / cm ²

Flexural strength
kg / cm

Compressive strength
kg / cm ²

Plain mortar 21 Polymer mortar 2 Mortar with polymer 49 and more organic 44 link 38 27 2 0.3 0.6 0.9

70
6th

170
164
94
87
8th
2
3
3

Under the chosen in this example Dampfaushärtungsbedingungen the strength immediately after curing with steam only about '/ io d ^he "o strength of the simple mortar was cured under the same conditions, whereas with an addition of an inorganic alkali compound -.um mortar the The initial strength is far higher than that of the polymer mortar and even higher than that of the simple mortar; at the same time the dimensional accuracy improves. It is noteworthy that the flexural strength, which contributes significantly to the overall strength, is considerably increased.

After 4 hours of steam curing, the strength is that of the polymer and an inorganic one Compound, such as lithium sulfate, lithium chromate or the like, mixed mortar already higher than the strength of ordinary mortar after curing with steam overnight (temperature increase from about 15 ° C per hour to 65 ° C, maintaining this temperature for 5 hours and gradually reducing the temperature to room temperature). This is a common process in the manufacture of molded articles.

So a mortar mixed with polymer and an inorganic alkali compound is used for production used by molded articles, productivity is greatly improved.

On the other hand, if an inorganic compound of a metal other than an alkali metal is used, fas? no effect at all or the strength even decreases, like 45
46
73
67
62
62
45
32
33
35

205
145
290
268
245
238
150
130
133
142

-0.01
-0.55

-0.005

-0.01

-0.01

-0.01

-0.05

-1.25

-0.56

-0.50

is apparent from the results of Table 3.

Example 3

A cement material composed of 100 parts of cement, 244 parts of sand and 327 parts of gravel with the monomers, the catalyst, 5 parts of inorganic compound and water in the values shown in Table 4 was prepared according to the JIS A-1132-1963 method (preparation of a specimen for strength tests) Mixed proportions. The mixture was molded into a concrete sample. After 2 hours, the mold containing the concrete sample was placed in a steam curing chamber. The temperature of the curing chamber was increased at a rate of 15 ° C per hour to 65 ° C, held at this value for 5 hours, after which the steam was removed. The concrete sample was allowed to stand in the chamber to cool, whereby a hardened concrete sample was obtained. After switching off the steam, the temperature was in the curing chamber at a speed of 6-10 ⁰ C per hour to room temperature (25 ° C).

24 hours after the completion of the molding, the mold was taken out of the curing chamber. The cured material was removed from the mold, and the compressive and flexural strength of the cured one Materials were determined according to JIS A-1108 and JIS A-1106 methods.

Furthermore, the samples were ^{cured in a room at 20 °} C. and 65% humidity for 4 weeks. The compressive strength and flexural strength were then measured again. The results are given in Table 4.

Table 4 Shares Water soluble Redox catalyst, Inorganic compound Water, Type of cured Water soluble networking Parts Parts Materials Ethylenic unge Monomer, parts saturated monomer,
Parts __ - - 60 - 57.7 Plain concrete Methylene-bis- ^ -Dimetbyl- K ₂ CO ₃ 57.7 Polymer concrete Acrylamide 1.26 acrylamide 0.24 aminopropio- Na ₈ Cr ₄ O ₄ · 10 H ₂ O Concrete with polymer nitrile 0.30 Na ₅₁ CrJsO ₇ · _{2H 2} O and more inorganic Sodium meth- Kalhimper Na ₈ WO ₄ · 2 H ₈ O link acrylate 0.18 sulfate 0.36 K ₂ SO ₄ Na ₂ Al ₂ (SO ₄ V 24 H ₈ O FeCl, -4 H ₂ O 57.7 Pb (NO ₈ ). CoSO ₄ -7 H ₂ O SnCl ₂ · 2 H ₂ O Al (NOs) ₃ -9 H ₂ O

13th 14th

Continuation of table 4

Type of hardened material

Strength immediately after releasing from the mold. Strength after 4 weeks

Flexural strength, compressive strength, flexural strength, compressive strength

kg / cm ² kg / cm ² kg / cm ² kg / cm ²

Plain concrete
Polymer concrete

Concrete with polymer and inorganic compound

28 13

42 50 36 46 49 44

10

14th

In this example, different types of concrete are cured with steam for a long time. Similar to the mortar in the previous example can be seen that the strength of the concrete material, which is only with mixed with the polymer is much lower than that of ordinary concrete, whereas the concrete material, which is mixed with the polymer and an inorganic alkali compound, excellent strength-259 155

356 392 294 390 384 366

148 160 142 159 156

even after prolonged curing with example 4

In a manner similar to Example 1, various mortar samples (see Table 5) were molded and cured in water at 20 ± 3 ° C.

The flexural strength and compressive strength of the cured samples are given in Table 5.

107 48 41 38 142 71 170 79 137 57 163 75 154 77 132 70 29 33 9 35 21 29 21 39 39 40 onarten properties as in Has steam.

Table 5

Mixing components and strength of different mortars

Type of hardened material Shares Sand,
Parts Mixing water, Parts Cement,
Parts 200 water 60 Plain mortar 100 200 Acrylamide
Sodium acrylate
1,3-di- (methacrylamidomethyl) -2-imide- 1.50
0.45
0.35 Polymer mortar 100 / S-dimethylaminopropionitrile
Potassium persulfate
water 0.24
0.30

Mortar with polymer 100

and K ₂ SO ₄

Mortar with polymer 100

and Na ₂ WO ₄ · 2 H ₂ O

Continuation of table 5

Parts of K ₂ SO ₄ were added to a solution in the same proportions as above, and the solution was used for makeup

Kj-SO ₄ was replaced with 5 parts of Na ₂ WO ₄ · 2 HgO in the above solution and the resulting solution was used for mixing

Type of hardened material Flexural Strength, kg / cm * after after after Compressive strength, kg / cm * after after after after 3 days 7 days 28 days after 3 days 7 days 28 days ITag 20th 33 56 ITag 95 167 302 Plain mortar 7th 29 41 76 34 76 140 210 Polymer mortar 17th 35 48 89 27 110 187 340 Mortar with polymer 20th 40 and K ₈ SO ₄ 33 45 86 106 176 328 Mortar with polymer 19th 38 and Na ₂ WO ₁ · 2 H ₂ O

Comparing the strength of the polymer mortar with that of simple mortar according to the above Example, after the mortars are hardened with water at normal temperature, one recognizes that that the polymer mortar has better flexural strength, but a considerably lower compressive strength than has simple mortar.

On the other hand, it can be seen that when an inorganic alkali compound such as potassium sulfate is added or potassium tungstate for the polymer mortar its compressive strength and also something in terms of its flexural strength compared to the mortar, the only contains the polymer is improved.

Comparative example 1

Table 6 shows the strengths of simple mortar and polymer mortar with the same composition as in Table 5 during curing in the atmosphere (at 20 ^° C. and 65% atmospheric humidity).

The samples were molded in a similar manner as in Example 4. 24 hours after molding, the mold was peeled off and the molding became immediately cured in the atmosphere.

Table 6

strength of simple mortar and polymer mortar during curing in the atmosphere

Type of mortar Flexural Strength, kg / cm ²
after after
1 day 3 days 15th
34 after
7 days after
28 days PRESSURE STRENGTH, kg / cm
after after
1 day 3 days 83
111 2
after
7 days after
2fc days Plain mortar
Polymer mortar 7th
19th 30th
47 51
90 30th
41 141
182 210
326

The table shows that the polymer mortar has excellent strength properties. already at Shows hardening in the atmosphere.

Example 5 and Comparative Examples 2 to 3

Using the same cement / sand ratio as in Example 1 of FR-PS 15 02 675 hardened cement materials were in the same Way as produced in the method according to the invention. The results obtained are as follows Table 7 given. From the results it can be seen that the properties of the invention Cement material are superior to those of the known polymer mortar .. In particular, the The difference in steam hardening is remarkable, since according to the method according to the invention, the time to Production of a hardened cement material abbreviated and thus its usability expanded can be.

Example 6 and Comparative Examples 4 to 5

Using the same cement / sand ratio as in Example 1, cured cementitious materials were prepared according to the above procedure. The properties of the cured cementitious materials are shown in Table 8 below, the amount of water used for mixing being selected to be most suitable for making a cement mortar.

Example 7 and Comparative Examples 6 to 7

Using the same ratio of cement to sand as in Example 6 of DT-OS 14 71 481 cured tearing materials were obtained; the properties of these materials were tested, the results obtained are shown in Table 9 below. From the results it can be seen that according to the method of the German Offenlegungsschrift, with the sodium silicate is present, although an increase in compressive strength compared to the process without sodium silicate according to JA-AS 4215/1969 can be achieved, but that the result of the erfindungseemäße Procedure differ from that of the German Offenlegungsschrift in a surprising way. It it should also be noted that the silicate used according to the German Offenlegungsschrift as a hardening retarder serves so that the results of the invention cannot be predicted.

Example 8 and Comparative Example 8

To demonstrate the technical progress of the

Method according to the invention compared to that from

the method known from GB-PS 10 65 053, a comparative test was carried out with the following results:

To a mixture of 500 parts by weight of port

land cement, 1000 parts by weight of sand, 300 parts by weight of water and 2 parts by weight of ammonium persulfate 50 parts by weight of a mixture of unsaturated polyester (60) and styrene (40) with a Content of cobalt naphthenate as hardening accelerator

niger given; these ingredients were mixed. Thereafter, the resulting mixture became a hardened cement material containing unsaturated polyester in the same manner as in Example 1 obtained. A simple mortar was also used

prepared using the same ingredients as above except that the unsaturated Polyester was not used. The strengths of the cured ones obtained in this way Cement materials were the following:

After a week pressure After a week pressure Air hardening strength Water hardening strength Bend kg / cin ² Bend kg / cm ¹ strength 9.0 strength 32.2 kg / cm ² kg / cm ^a Approx 3.1 3.3 satiated polyester contain 191.3 191.0 the mortar Easier 30.8 43.0 mortar

18th

The air curing was carried out at 2O ⁰ C and a humidity of 65%, and the curing m water at ± 3 ° C.

From a comparison of the above results with the effect according to the invention is clear show that the method according to the invention compared to the British patent has a technical Showing progress.

In addition, the above vergle.ch.test found that the mixture of unsaturated polyester and mortar prior to curing «N exhibited very poor flow behavior, such as bemV while that of simple mortar with 100 was, w * processability of the un-

AECAE ^ containing mortar strong herabt "The flow behavior of the Zementmatenals geder invention is before has hardened, on Ä the giichen ^g standards about 97. It is followed by a further advancement of the process according to the invention over the 1bnt.schen from the patent specification 10 65 053 the known process.

Table 7

composition

(Cew parts)

Z: - sand water: r for mixing

rrn.:nt

Properties of the hardened material after steam hardening

Compressive strength tensile strength »

(kg / cm =) * g / change)

immediately after immediately after (A) after 28 after 28 days of formation

(1 day) (1 day)

Properties of the hardened
Materials after water hardening
Compressive strength Tensile strength Length (kg / cm ¹¹ ) (kg / cm =) change

immediately after immediately after (%) after 28 after 28
For days For days
mung mung

(1 day) ^ (1 Tae)

Remarks

70 calcium sulfate Iu
Ammonium persulfate 2

aqueous solution
of acrylamide:
Formaldehyde = 94
1: 1.2 (molar ratio)
Diethylaminopropionitrile 0.2
additional Water 20

70 acrylamide 2.1 266
Sodium methacrylate 0.2
Sodium acrylate 0.2
Methylenebisacrylamide 0.3

/? - dimethylaminopropionitrile 0.4
Potassium persulfate 0.4
Sodium sulfate 10
Water 72.6

Table 8

Polymer mortar according to FR-PS 15 02 675

682 32 0.03 82 698 9 93 0.03

Mortar according to the invention

composition

(Parts by weight)

Ze- sand water

ment to mix

Compressive strength (kg / cm ^s ) immediately after molding (1 day)

Remarks

after

28

Days Table 8 (continued)

composition

(Parts by weight)

Ze- sand water

ment to mix

Compressive strength (kg / cm «) immediately after molding (1 day)

Remarks

after

28

Days

1.00 300 water 40 86

300

Calcium sulfate 5.5
Ammonium persulfate 1.1
44% aq. Solution of acrylamide: formaldehyde = 1: 1.2
(Molar ratio)
51.8

Diethylaminopropionitrile 0.1
additional
Water 11.0

245 simple mortar

Polymer mortar according to the 208 FR-PS 15 02 300

Acrylamide 1.1
Sodium methacrylate 0.1
Sodium acrylate 0.1
Methylenebisacrylamine 0.15
/? - dimethylaminopropionitrile 0.20
Potassium persulfate 0.20
acid sodium sulfate 5.0
Water 38.2

139

310

Mortar according to the invention

20th

Table 9 composition

(Parts by weight)

Ze-sand water for mixing

Properties of the cured material after steam curing Compressive strength Bending strength (kg / cm ¹ ) (kg / cm ² )

immediately after immediately after after 28 after

Forming (ITa ₆ )

Days forming (1 day) Days

Properties of the hardened Materials after water etching

Length Compressive Strength Bending Strength Change in Length (kg / cm ¹ ) (kg / cm *) change

(%) immediately after immediately after (%)

after 28 after 28

For-

mung

(ITag)

Days forming (!Day)

Days

200 water 82

78

46 23 50 0.01 35 316 8

200 Sodium 5Cat 4 Water 20
25% aq. Magnesium methacrylate solution 80
10% aq. Potassium persulfate 2

200 acrylamide 2.1 sodium acrylate 0.7 1,3-di (acrylamidomethyl) - 2-imidazolidone 0.5 0-dimethylaminopropionitrile 0.3 potassium persulfate 0.4 potassium sulfate 7 water 78

223 18

1.25 50 289 16

0.01
0.16

390 0.01 65 396 22 79 0.01

simple mortar

Polymer mortar according to DT-OS 14 71481

Mortar according to the invention

Compilation of the mentioned industry standards

1. JIS R-5201-1964;

2. JIS R-5201-1967;

3. JIS A-1124-1957;

4. JIS A-1132-1963;

5. JIS A-1198;

6. JIS A-1106.

Claims (10)

Patent claims: 1. Process for the production of hardened cement material using cement, Water, a water-soluble ethylenically unsaturated monomer, another water-soluble one Monomers, water-soluble inorganic alkali metal compound and a redox catalyst system, characterized in that a base material made of cement, optionally with aggregates, "water to make up." of the cement material and (a) 2 to 30% by weight (based on the water) of the ethylenically unsaturated Monomers and (b) 0.02 to 20% by weight (based on the water) of the further monomer with a catalytic amount of the redox catalyst system in the presence of a water-soluble one inorganic alkali metal compound from the group of oxides, hydroxides, sulfates, Metasiilfites, pyrosulfates, carbonates, chromates, bichromates, aluminates, tungstates, stannates, Orthophosphates, tripolyphosphates, manganates, phosphorus molybdates, phosphotungstates and / or aluminum alum and / or in the presence of potassium chrome alum in water or steam hardens, v / obei these alkali metal compounds in the case of oxides and hydroxides in Quantities of 0.5 to 10 wt .-% and otherwise used in quantities of 2 to 40 wt .-%, based on the amount of water used for mixing. 2. The method according to claim 1, characterized in that there is used as the alkali metal compound Potassium aluminum alum used. 3. The method according to claim 1, characterized in that that the alkali metal compound used is sodium sulfate, carbonate, bichromate, tungstate and / or potassium sulfate is used. 4. The method according to claim 1, characterized in that the ethylenically unsaturated Monomers »at least one compound from the group acrylamide, N-methylolacrylamide, methacrylamide, N - methylol methacrylamide, acrylonitrile, hydroxymethyl methacrylate, methacrylic acid, their metal salts, acrylic acid and their metal salts are used. 5. The method according to claim 4, characterized in that the ethylenically unsaturated Monomer is a mixture used, the larger part of acrylamide and the smaller part Part of at least one compound from the group consisting of sodium acrylate and sodium methacrylate is composed. 6. The method according to claim 1, characterized in that the water-soluble crosslinking agent Monomer at least one compound from the group methylenebisacrylamide, 1,3 - di - (acrylamidomethyl) - 2 - imidazoline, 1,3 - di - (methacrylamidomethyl) - 2 - imidazolidone, hexahydrotriacryloyliiriazine, Diacrylamidodimethyläther and / or Dimethylacrylamidodimei.hyläther used. 7. The method according to claim 1, characterized in that there is used as the oxidizing component of the redox catalyst system at least one compound from the group consisting of potassium persulfate and Ammonium persulfate is used. 8. The method according to claim 1, characterized in 7eichne1 :. that at least one compound from the group consisting of triethylenetetramine, hexamethylenediamine, dimethylaminopropanol, nitrilotrispropionamide, β- dimethylaminoethanol, β-dimethylaminopropionitrile, / J-diketone and sodium formaldehyde sulfoxylate is used as the reducing component of the redox catalyst system. 9. Process according to claims 7 and 8, characterized. That the catalyst used in amounts of 1 to 30% by weight, based on the polymerizable components. 10. The method according to any one of the preceding claims, characterized in that one an aqueous solution containing the monomers and the reducing component of the redox catalyst system contains, and an aqueous solution that is the oxidizing component of the redox catalyst system and contains the inorganic alkali metal compound mixed together and immediately added to the base material composed of cement or cement and aggregates and mixed with it.