CS231635B1 - Modified cementitious clinker hydraulic binder - Google Patents

Abstract

The invention provides a hydraulic binder with an adjustable initial setting time. The modified hydraulic binder is based on a mixture consisting of 85 to ;K/»S9\ parts by weight of ground cement clinker, 0.1 to 10 8' parts by weight of carbonate, hydrogen carbonate, hydroxide, silicate, hydrogen silicate, hydrogen sulfite or a/ alkali metal oxylate, 0.1 to 5 parts by weight of a salt of a condensation product of a mixture consisting of at least half of phenol and at most half of the sulfonation product of /5-naphthol, of which at most 70 8 acid groups are contained by a trivalent cation from the group of metals iron, clay or/and chromium and dae. Ie at least 17 - parts by weight of mixing water. The salt of the condensation product may also be partially oxidized.

Description

The invention relates to a hydraulic binder based on cement clinker, ground without the addition of gypsum, and solves the problem of the composition of the binder β with an adjustable start of setting and has a flow-through ability,

CS copyright certificates No. 225 063 ^and 225 064 (PV 6325-80 and 6326-80) it is known to produce binders based on silicates without the addition of gypsum by mixing 0.1 to 10% by weight of carbonate, bicarbonate or hydroxide of an alkali metal or alkaline earth metal and 0.01 to 5% by weight of a condensation product of sulfomethylated phenols with formaldehyde, the acid groups of which are up to 70% occupied by a trivalent cation from the group of metals iron, aluminum or chromium, or the same amount of the same product, which was further oxidized by the action of oxygen* These binders have a delayed onset of setting after the addition of mixing water, but this is not completely controllable.

It has been found that the aforementioned deficiency is alleviated by a modified hydraulic binder based on cement clinker, the essence of which consists in containing 85 to 99.89% by weight of ground cement clinker, 0.1 to 10% by weight of carbonate, hydrogen carbonate, hydroxide, silicate, hydrogen silicate, hydrogen sulfate, hydrogen sulfite or/and alkali metal oxalate, 0.01 to 5% by weight of a salt of a condensation product of a mixture consisting of at least half of phenols and at most half of the sulfonation product of β-naphthol, of which at most 70% of the acid groups are occupied by a trivalent cation from the group of metals iron, aluminum or/and chromium, and at least 17% by weight of mixing water.

231,635 Preferably, the salt of the condensation product may be oxidized by the action of at least 0.5% by weight of oxygen, based on the weight of the phenols in the condensation product.

The binder according to the invention can be used to achieve the desired initial setting time by selecting the amount of salt of the condensation product added. At the same time, it has a higher self-leveling ability compared to other known binders at the same mixing water content.

The essence of the invention can be seen from the examples of embodiments, to which the invention is not limited in any way. The stated % are by weight.

Example 1

192 g of /3-naphthol and 154 g of sulfuric acid £6ijni were introduced into the sulfonation flask. Sulfonation was carried out at a temperature of 110° to 115°C for 30 minutes with stirring. A solution of 300 g of diphene with a content of 82% pyrocatechin in 300 g of water was prepared in a condensation vessel equipped with a stirrer and with the possibility of heating and cooling. The sulfonate of /^-naphthol, prepared according to the previously mentioned procedure, was added with stirring and the temperature was adjusted to 40° C and 208 g of formaldehyde 36Sc _w ni were gradually added over 120 minutes. The temperature was maintained in the range of 45 to 60° C. After the addition of formaldehyde was completed, stirring was continued for another 60 minutes and then 200 g of NaOH 40'j^ni were added. Subsequently, 120 g of FeClg 40£ solution was added. This product, designated as product A, was used as a plasticizer. The structure of condensation product A can be represented by the formula?

where Me denotes Fe ³ *, Al ³ *, Cr ³ * or Na*.

I

Example 2

231,833

The butyl phosphate of [alpha]-naphthol was prepared in accordance with Example 1.

In a condensation vessel, 188 g of phenol was dissolved in 200 g of water, p-naphthol sulfonate was added and condensed for 3 hours at 50 to 80° C. Then it was allowed to stir for another 60 minutes, cooled to 50° C and 200 g of 40% NaOH were added.

After stirring the mixture, 100 g of 35% Cr ₂ (60 ₄ ) ₂ was added with constant stirring. This product was designated as product 3 and was used to prepare the binder, the structure of product B can be described by the formula:

where Ke represents Fe^*, Al^*, Cr^* or Na* and n is 0 to 2.

Example 3

For the preparation of the cement slurry, cement clinker from the Hranice cement plant was used, ground to a specific surface area of 700 m/kg in the presence of 0.3% sodium lignin sulfonate. From this cement, a freely flowing slurry was prepared with the addition of 1% Na ₂ C0g and 1% product A, with the addition of 26% mixing water. The slurry began to set after 7 hours. After hardening, the slurry reached a compressive strength of 13.7 MPa after 1 day, 38 MPa after 7 days and 120 MPa after 28 days.

Example 4

The same cement slurry was prepared as in Example 1. A slurry with 26% mixing water and a free-flowing consistency was prepared by adding 1% Na ₂ C0g and 1% product B. This slurry began to set after 15 minutes and reached a compressive strength of 58 MPa after 1 day, 57 after 7 days and 100 tlPa after 28 days.

Example 5

231,839

For the preparation of cement slurries, cement clinker from the Štramberk cement plant, ground to a specific surface area of 700 m2/kg, and clinker from the Hranice cement plant, ground to a specific surface area of 3S20 m2/kg, were used as cement. The slurries had a liquid character. The ratio of mixing water to cement is indicated by the symbol w.

cement ingredients beginning of solidification W Stramberg lye Na ₂ C0 ₃ ♦ i;j, product A 3.5 hours 0.22 1.45c NaHCO3 ♦ lj _w product A 5 hours 0.23 '15^ !;'3 ₂ 0ί0 ₃ -1 1JJ product A 2 hours 0.23 Borders 15- Na ₂ C0 ₃ ♦ 15 _d product A 28 hours 0.27 25J f:a ₂ C0 ₃ ♦ 0.3/ product A 24 hours 0.30

Example S

Similar to example 5, for the preparation of cement

used porridge product 3. cement ingredients beginning of solidification w Stramberg 15; Na ₂ C0 ₃ ♦ product 3 5 minutes 0.25 ♦ Borders 15J Na ₂ C0 ₃ ♦ 1% product 3 20 minutes 0.27 15. KaHC0 ₃ ♦ 1% product 3 30 minutes 0.27

The binder according to the invention is preferably intended for the production of precast products on lines.

Example 7

231,633

For the preparation of cement slurries, clinker from the Lochkov cement plant was ground in the presence of 0.2 wt. % sodium lignin sulfonate as a grinding additive. The ground clinker had a specific surface area of 700 o

m /kg. First, a test was carried out with the preparation of a slurry sw=0.22, when 1% Na ₂ C0 ₃ dissolved in mixing water was added to the ground clinker. The mixture prepared in this way was completely unworkable. 1% of the product was added to the same ground clinker

A prepared according to example 1, which was dissolved in the mixing water and a test was carried out with the preparation of a slurry ow=0.22. This mixture was very difficult to process. When preparing a slurry ow=0.22, when 1% Na ₂ C0 ₃ and 1% of product A were dissolved in the mixing water, the slurry had a freely flowing character. The viscosity of the slurry measured on a rotational viscometer at a speed gradient of 90 s was 1.2 Pa.s. This cement slurry, when measured on a Theological instrument, which allows the detection of hysteresis Theological curves, practically did not show a flow limit. This mixture also differed from the slurries of conventional Portland cements, which have a flow limit.

Example 8

Similar to the previous example, the procedure was followed when using clinker from _{the Lochkov cement plant, which was ground to a specific surface area of 350 m2/kg. When preparing a cement slurry ow=0.22 using 1.5% Na2CO3} ^and _0.75 % product B, prepared according to example 2, similar results were achieved.

The binder according to the invention can be used primarily where it is expedient to use as little mixing water as possible.

Claims (3)

SUMMARY OF THE INVENTION 231 83S Modified hydraulic binder based on cement clinker ground to a specific surface of 150-3000 m m / kg and having 5 to 95 parts by weight of less than 5 µm, additives based on a mixture of a salt of a sulfomethylated phenol-formaldehyde condensation product. the acid groups of which are up to 70 occupied by a cation from the group of iron, aluminum or chromium, optionally oxidized by oxygen and carbonate, acid carbonate, hydroxide, silicates, acid silicate, acid sulphate, acid sulphite and / or alkali metal oxalate, 86 to 99.89% by weight of cement clinker, 0.1 to 10 wt _Zu carbonate, bicarbonate, hydroxide, silicate, acidic clay, bisulfate, bisulfite and / or an alkali metal oxalate, from 0.01 to 5% by weight salts of condensation a product of the mixture consisting of at least half of the phenols and at most half of the sulphonation product of β-naphthol, of which at most 70 acid groups are occupied by a trivalent cation from the group of metals iron, aluminum and / or chromium; 2. The binder according to claim 1, wherein the phenol is a dibasic phenol. 3. The binder of claim 2, wherein the dibasic phenol is pyrocatechin.