CS231635B1 - Modified hydraulic binding agent on clinker base - Google Patents

Abstract

The invention solves the hydraulic binder with adjustable time of solidification. The modified hydraulic binder is based on mixtures consisting of 85 to K / S9 \ t weight of ground cement clinker, 0.1 to 10% by weight of carbonate, acidic carbonate, hydroxyl, silicate, acidic silicate, acid sulphite or [alpha] alkali oxalate metal, 0.1 to 5% by weight of a condensation salt the product mixture, consisting of: of at least half of the phenol and at most half sulfonation product, 5-naphthol, of which more than 70 8 acid groups are contained by a trivalent cation from the group iron, clay, and / or chromium metal and dane. Ie of at least 17% by weight of mixing water. Sul condensation product may be also 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 binder composition by an adjustable setting of the setting time and has an eamoating ability,

It is known to produce silicate-based binders without the addition of gypsum by adding 0.1 to 10% by weight of carbonate, acid carbonate, to the ground cement clinker, according to the author's certificate No. 225 063 ^and 225 064 (PV 6325-80 and 6326-80). or an alkali metal or alkaline earth metal hydroxide, and from 0.01 to 5% by weight of a condensation sulfomethylated phenol product with formaldehyde, the acid groups of which are up to 70% occupied by a trivalent cation from the group of iron, aluminum or chromium; These binders have a delayed onset of solidification after addition of the mixing water, but they are not fully controllable.

It has been found that a modified hydraulic cementitious binder based cement comprising 85 to 99.89% by weight of artificial cement clinker, 0.1 to 10% by weight of carbonate, bicarbonate, hydroxide, silicate , an acidic silicate, an acid sulphate, an acid sulphite and / or an alkali metal oxalate, 0.01 to 5% by weight of a salt of a condensation product of a mixture consisting of at least half phenols and at most half sulphonation product β-naphthol a trivalent cation from the group of metals of iron, aluminum and / or chromium and at least 17% by weight of the mixing water.

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

With the binder of the invention, the desired setting time can be achieved by selecting the amount of salt of the condensation product to be added. At the same time, it has a higher self-spreading ability over other known binders with the same mixing water content.

The invention is illustrated by the following non-limiting examples. The stated% are by weight.

Example 1

To the sulfonation flask was charged 192 g of β-naphthol and 154 g of sulfuric acid £6. While stirring, it was sulfonated at 110 ° to 115 ° C for 30 minutes. In a condensation vessel equipped with a stirrer and with the possibility of heating and cooling, a solution of 300 g of diphene containing 82% pyrocatechin in 300 g of water was prepared. Under stirring, n-naphthol sulfonate prepared according to the above procedure was added and the temperature was adjusted to 40 ° C and 208 g of formaldehyde 36Sc _{w / w} was added gradually over 120 minutes. The temperature was maintained at 45-60 ° C. After the addition of formaldehyde was complete, it was stirred for a further 60 minutes and then 200 g of NaOH (40%) were added. Subsequently, 120 g of a FeClg solution of 40% was added. This product, designated product A, was used as a plasticizer. The structure of the condensation product A can be represented by the formula?

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

ί

Example 2

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The .beta.-naphthol bulphonate was prepared in accordance with Example. 1.

188 g of phenol was dissolved in 200 g of water in a condensation vessel, the .alpha.-naphthol sulfonate was added and condensed at 50-80 DEG C. for 3 hours. The mixture was then allowed to stir for 60 minutes, cooled to 50 DEG C. and 200 ml. g of NaOH 40%.

After stirring the mixture, 100 g of 35% Cr ₂ (0O ₄ ) ₂ was further added with stirring. This product was designated product 3 and was used to prepare a binder, the structure of product B can be represented by the formula:

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

Example 3

Cement clinker from the Hranice cement factory ground to a specific surface of 700 m / kg in the presence of 0.3% sodium lignin sulphonate was used to prepare the cement slurry. A free-flowing slurry was prepared from this cement with the addition of 1% Na ₂ CO ₂ and 1% of product A by adding 26% mixing water. The onset of slurry solidification was 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 centent as in Example 1 was used to prepare the cement slurry. With the addition of 1% Na ₂ CO ₂ and 1% of product B, a slurry was prepared with 26% mixing water, of free-flowing consistency. This slurry had an initial setting of 15 minutes and reached a compressive strength of 58 MPa after 1 day, S7 after 7 days and 100 tPa after 28 days.

Example 5

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For the preparation of cement pastes, cement clinker from cement plant Štramberk, ground to a specific surface of 700 m / kg and clinker from cement plant Hranice ground to 2 specific surface of 3S20 m / kg were used as cement. The porridge was liquid. The ratio of mixing water to cement is indicated by the symbol w.

cement additives the beginning of solidification W Štramberk Na ₂ C0 ₃ Product A 3.5 hours 0.22 1.45c NaHCOg Produkt lj _w product A 5 hours 0.23 '15 ^!; '3 ₂ 0 ₀ 0 -1  1JJ product A 2 hours 0.23 Border 15 - Na ₂ C0 ₃ ♦ 15 _d product A 28 hours 0.27 25J f: a ₂ CO ₃ ♦ 0.3 / product A 24 hours 0.30

Example S

As in Example 5, it was used for the preparation of cement

used product 3. cement additives the beginning of solidification w Štramberk 15; Na ₂ C0 ₃ ♦ product 3 5 minutes 0.25 ♦ Border 15J Na ₂ C0 ₃ ♦ 1% product 3 20 minutes 0.27 15. KaHCO ₃ ♦ 1% product 3 30 minutes 0.27

The binder according to the invention is preferably intended for the production of prefabricated elements on the lines.

Example 7

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To prepare the cement slurry, clinker from the Lochkov cement plant was ground in the presence of 0.2 wt. sodium ligninsulfonate as grinding aids. The ground clinker had a specific surface area of 700 o

m / kg. Initially, a slurry preparation w = 0.22 was carried out by adding 1% Na ₂ CO ₃ dissolved in the mixing water to the ground clinker. The mixture thus prepared was completely unprepared. covatelná. 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 slurry preparation ow = 0.22 was carried out. This mixture was difficult to process. In the preparation of the slurry ow = 0.22, when 1% Na ₂ CO ₃ and 1% product A 1 were dissolved in the mixing water, the slurry had a free-flowing character. The viscosity of the slurry measured on a rotary 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 hysteresis of the theological eyeball to be read, did not show practically a flow limit. This also distinguished the slurry from conventional Portland cements having a flow limit.

Example 8

As in the previous example, the clinker from the Lochkov cement plant was used, which was ground to a specific surface of 350 m ² / kg. Similar results were obtained when preparing the cement slurry ow = 0.22 using 1.5% Na ₂ CO ₃ and 0.75% of product B prepared according to Example 2.

The binder according to the invention can be used in particular 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.