DE2412352A1 - IMPROVED HYDRAULIC CEMENT AND METHOD FOR MANUFACTURING IT - Google Patents

Description

Patent attorneys: 2412352 Dr. Ing.Waltsr Abitz

Dr. Dioter f. Morf March 14, 1974

Dr. Hans-A. Erauns 34-1 301

8 Bünctum SS, Pianzarauerair. 28

RAYCHEM CORPORATION

300 Constitution Drive, Menlo Park, Calif. 9 * 1025,

V. St. A.

Improved hydraulic cement and method of making it

The present invention relates to cements and provides cement compositions, inter alia, an improved Have shelf life when stored in the open.

Since their first invention by the Romans, hydraulic cements (i.e., those cements made by the chemical reactions that occur when mixed with large amounts of water, solidify and harden) in connection used with various aggregates in building. The term "cement paste" is used herein with reference to the "plastic Mixture used, which results in the combination of a dust-like hydraulic cement with large amounts of water results. "Mortar" results when cement paste is combined with a relatively fine aggregate such as sand becomes, while "concrete" means the union of both fine and

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also, coarse aggregate, such as broken rock, with cement paste arises. By 1963 the world consumption of concrete was up an estimated three thousand million tons increased. Although part of this concrete is hydraulic Cements, such as high alumina and slag cements, were considered to be in by far the largest proportion of the total Cement Ingredient Portland cement is used, a material traditionally made by firing a ground mixture from limestone and clay or slate to clinker, which is mainly composed of calcium aluminates, silicates and aluminoferrites composed, manufactured. The clinker is then ground, usually with a few percent of one or more of the calcium sulfate forms as a co-ground supplement. Portland cements are used by the American Society of Testing Materials (ASTM C-150-72) various in five main "types" are divided into the heat of hydration, the green strength and the sulphate resistance differentiate. Portland cement types 1 and 11 are the most common; Type 1 is for use in the present Invention particularly suitable

It usually takes 48 parts of water to thin 100 parts of cement. Since typically only about 25 parts of water chemically combine with the cement, a considerable amount of pole-forming water remains and, as a result, the hardness, compressive strength and durability characteristics of the set and hardened cement are reduced. It has clearly been proposed to combine organic substances known as water-reducing admixtures with other cement paste, mortar or concrete slurry constituents. These admixtures make it possible to achieve useful degrees of plasticity at lower water-cement ratios and typically reduce the water content by 10 to 14 % , so that types of concrete and the like can be achieved that have greater compressive strength, hardness and retention.

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have availability. Usually special admixtures in addition to that they control the water demand also reduce the solidification and hold the concrete during the entire period while it is being put in place becomes processable, so that deformation cracks, cold joints and other irregularities are avoided.

Among the first admixtures that reduce the water requirement, which have been proposed, the condensed aromatic sulfonates of US Pat. No. 2,141,569 were mainly found Formaldehyde condensates of naphthalene sulfonates. In US Pat. No. 2,690,975, however, these agents are characterized that they have found virtually no commercial use because they were unable to 1 to 3 day initial strengths and to significantly increase the breaking strength; they are also not used by the admixtures Committee of the American Concrete Institute (ACI) in its report "Admixtures for Concrete" Journal of the Am. Concrete Inst. 60, 1481 (Nov. 196 $) mentioned among the four classes of materials for use for degradation of the water demand are generally available.

So far, admixtures with cements have essentially been combined in four different ways: (1) Drier Aggregate (US Pat. Nos. 2,311,289 and 2,360,518) or aggregate in aqueous solution to cement clinker during grinding (U.S. Patent 2,141,570); (2) dry mixing with dry, ground cement prior to use in mortar or concrete; (3) dry aggregate to concrete or mortar slurry; or (4) aggregate in the mixed water to the dry cement. Generally speaking, the literature (e.g. US Pat. No. 689,294) indicates that the order of addition is little or no has no significance at all, although the ACI committee for admixtures (cf. the above-mentioned report on page 1493) warns against liquids that contain admixtures, in contact with the cement before adding the mixed water to let come.

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By the present invention, hydraulic cement containing, dust-like masses provided, which are produced by a novel process in which a solution that an effective amount of a condensed naphthalenesulfonic acid or a salt thereof which increases the plasticity in open storage contains, in dusty, hydraulic cement, without significantly increasing the specific Blaine surface of cement, evenly mixed in, so that a dusty, treated cement that exhibits unique properties when mixed with water yields the additional naphthalene sulfonate or contains another additive reducing the water requirement, prepared and optionally with the formation of a cement paste, a mortar or concrete is aggregated. Preferably, the cement particles are only condensed with the naphthalenesulfonic acid or substantially coated with the salt.

The mass according to the invention can be used alone or together with cement masses, which have not been treated according to the invention can be used. In addition, the masses can be further free, condensed naphthalene sulfonate or other substances that reduce the water requirement. When the cement to be used for the production of foamed lightweight concrete, it is preferable to use the cement compositions according to the invention to be used without the addition of additives that reduce the need for free water. On the other hand, if it is more normal Concrete is to be produced, it is preferable to add such additives which reduce the water requirement.

By using the compositions treated according to the invention, a reduction in the water requirement is achieved to a degree that considerably exceeds that which can be achieved if a comparable amount of the additive is used in a conventional manner. Cement paste made from the new, treated cements, Mortar or concrete slurries show, when used with other free admixtures,

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noticeably improved consistency and plasticity (i.e. they show a stronger Newtonian behavior than similar masses, which contain free admixtures and normal types of cement), so that it is easier to work with. Thus relates an effective open storage plasticity increasing amount as used herein is effective for improvement in relation to normal combinations of cement and free additives or admixtures. The inventive wet mixes generally have a controlled shelf life in open storage, during which the rate at which its viscosity increases is much slower than it is for conventional mixtures are normal, and yet they set in about the normal amount of time. Once they are frozen they tend to set faster than normal and fully cured products made from the treated cements show superior properties compared to the properties of products made with or without untreated cement conventional chemical additives have been made, in particular are the freeze-thaw resistance and the compressive strength of foamed lightweight concrete from the inventive Cement was produced, much larger than it. achievable with conventionally used concrete mixes are.

The manner in which these and other objects and advantages of the invention are achieved will be apparent from the following, ins single detailed description and from the enclosed drawings. In the drawings, the 1 to 8 show the change in viscosity with time of compositions produced according to the invention in comparison with the compositions of the State of the art graphically. This viscosity change. is described in more detail in the examples.

Although the invention is not considered by the following theoretical Declaration is to be viewed as limited, it is to be assumed that the surcharges, if they are as with the present

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Invention are applied to the surfaces of the cement particles can be adsorbed. Though the fact or the extent of such adsorption has not been accurately proven could be, such adsorption appears likely from the observation that heat when mixed being developed (which may indicate a chemical reaction) and, perhaps more significantly, that Grinding the treated powdery cement the beneficial Properties that are otherwise given to the product can be markedly weakened, if not canceled. the end For the reason given last, the mixing of the cement with the aggregate is carried out in the first case under conditions in which milling is essentially avoided. That means that mixing the specific surface according to Blaine of the powdery cement, determined according to the ASTM procedure C-2Q4-72, should not increase so significantly, that the gain of the advantages of the invention is usefully prevented. Most preferred is mixing to be accomplished without applying significant shear stress, d. H. without the 'specific surface area according to Blaine, as determined within the precise limits of ASTM Procedure C-204-72 will. It goes without saying, of course, that an increase in the specific surface area according to Blaine, which on a mere gradual change, with it the degree to which the advantages of the invention are ensured, adversely affected; the preferred Blaine specific surface areas can range from about 2500 to about 4000 Increases in Blaine levels on the order of 200 to 300 cm / g are allowed.

The aggregate compounds used in the treatment of dry, dusty cement according to the present invention are used are those which have the characteristic unit

- CH - A (SO, M) _V

I * ^x

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in which R is hydrogen or alkyl, A is substituted or unsubstituted naphthalene, M is hydrogen or any other cationic radical, "for example ammonium, alkali or alkaline earth metal (e.g. sodium, potassium or Calcium) or amine (e.g. dimethyl amino or diethyl amino), and χ is an integer of 1 Ms 3 »preferably 1,". The aforementioned unit is connected to at least one other

A (SO ₇₁ M) share via the alkylene group, ie CHR group, y χ

and in the case of the more highly condensed naphthalenesulfonates, which are preferred here, it serves as a characteristic, repeating unit. Advantageously, the aggregate compound has at least four such repeating units (ie a “degree of condensation” of four or more, preferably of about seven). If M is multivalent, it is of course _{bound to a -CH-A SO 7} - unit for each valence. The nature of M is not critical,

and essentially any cation which does not render the aggregate compound insoluble can suitably be used be used.

The aggregate compounds result from the condensation of naphthalene sulfonic acids or sulfonates with compounds which have the divalent carbonyl radical> C = 0, such as ethylene urea or aliphatic ^ aldehydes, e.g. formaldehyde, acetaldehyde or isobutyraldehyde. The number of carbon atoms in the condensate residue, d. H. of group R, is insignificant, except that it is limited by the condition "that the condensate is in the carrier solvent must be sufficiently soluble for the purpose of the invention.

Special procedures for the preparation of suitably condensed naphthalene sulfonates can be found, for example, in DT-OS 1 960 812 (Chem. Abstr., 2H 1304-54-k (1971)) and in US Pat. Nos. 2,141,569, 2,690 975, 2,529,602, and 3,277,162. To the revelations of each of these

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Reference is expressly made here to publications. A particularly preferred condensate is that condensed with formaldehyde Naphthalene Sodium Sulphonate (MWrS ^ OO), available from the Diamond Shamrock Corporation (Nopco Chemical Div.) Under the name "Lomar D."

As indicated above, one advantage provided by the present invention is the increased plasticity of open storage. The expression "open storage time ^11" , as used here, is the period of time that follows the dressing with water but before solidification (it is determined in accordance with ASTM C-191-71).

The aggregates can be used in "coating" dry cement in effective amounts increasing plasticity in open storage which are insufficient to significantly retard setting, these amounts generally being from about 0.01 to about 1.0 % By weight, based on the weight of the dry cement, is sufficient. (It should be noted that "dry" cement, as it is conventionally obtained and used, contains in the order of magnitude free absorption water in an amount of 2.5 wt For general purposes, a preferred range of the proportion of the aggregate for a "coating" is from about 0. $ to about 0.5%, while for foamed lightweight concrete the aggregate is preferably used in amounts ranging from about 0.01 to about 1.0% by weight, and most preferably from about 0.05 % to about 0.3 % .

Unless the treated cement is to be used for the production of foamed lightweight concrete, the Aggregate "coated" cement used together with conventional water-reducing agents, which are applied in a conventional manner, for example

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by dry mixing with "treated cement" or by adding with top-up water when preparing pastes, mortars and concrete slurries ». Such free surcharges can for example for cements with Blaine values from 3000 to 3500 in amounts of about 0.2 to about 0.6% by weight, based on dry cement, while the use of larger quantities unduly retards the setting can. ,

It will be understood that material which is in excess of the preferred upper limit of the proportion for coating of dry cement is used simply to an allowable extent as the need for free water degrading surcharge can work. In practice, these upper limits are set by the conditions that (a) material used in coating, dissolved in the coating carrier; and (b) the amount of used Solvent is less than the amount that causes clumping, caking or other harmful There are changes in the dusty state of the cement charge. So the carrier for the soluble aggregate, which is used in coating, preferably in amounts ranging from about 0.1% by weight to about 1.5% by weight, based applied to dry cement, rich. Can be used cement mixes with different amounts of additive have been treated separately. Water is the preferred carrier, although other suitable condensed naphthalenesulf onate solvents, such as dimethyl sulfoxide (DMSO), alternatively can be used.

Another consideration when measuring to achieve optimal results is the specific surface of the cement feed material. Cements that have a specific surface area according to Blaine

ο in the order of about 3000 to 3500 cm / g, ' are most common in the present invention, and the proportions given above result as found has been given the best results using such a cement.

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Reduced aggregate amounts can be used for cements with a low specific surface area according to Blaine, while increased proportions may prove to be most suitable for finer cements. For example, suitable proportions of formaldehyde-condensed naphthalene sulfonate when used in coatings can be characterized in that they are within the range from about 0.003 to about 0.28% by weight (based on dry cement), per 1000 Blaine units , while carrier water used in the coating is in the range of about 0.014 to about. 0.85% by weight (based on dry cement) per 1000 Blaine units can be added. Accordingly, over the range of 2000 to 70000 cm / g Blaine area, the aggregate material used can range from about 0.006 % (low Blaine value) to about 2% (high Blaine value) and water from about 0.03 % (low Blaine value) Value) to about 6% (high Blaine value).

Once mixing has been completed, the coated cement should preferably be kept at ambient temperature for at least about 15 minutes, and preferably about 3 Let it age for up to 24 hours before using large amounts of water in the manufacture of pastes, mortars or concrete slurry is prepared. As shown in the examples, coated cement does not appear to be has aged so as to exhibit properties more like those obtained when one is the same Amount of aggregate is added in a conventional manner, for example by adding in free form to the aqueous Mixture.

The following examples in which (as throughout the description and claims) all parts and percentages based on weight and all percentages are based on the weight of the dry cement, provided that no other information is specifically given,

. - 10 -

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chen the invention. The viscosities are measured with the Brookfield viscometer No. 4 determined at 24 ° C. All Rockwell hardnesses were given with a 12.7 mm ball and a maximum Load of 14.4 kg measured.

B e is ρ ie 1 1 .

Cement paste control sample (no additives )

a. 48 parts of water: 100 parts by weight of Portland cement type 1 were mixed thoroughly with 48 parts of water. The resulting slurry had what was considered to be workable consistency. The initial viscosity was approximately 3000 cps. After 45 minutes the viscosity of the pulp was about 5500 and it was very thixotropic in nature. Samples of this material were cured at room temperature in a 100 % relative humidity atmosphere. The samples had the following average hardnesses as measured. on the Ro CkWeIl- ¹¹ BIaCk "or C-scale to: 83.6 - 3 days; 88.5 - 7 days; 90.6 - 12 days.

b. 40 parts of water: The experiment described above was repeated using only 40 parts of water instead of 48. The resulting slurry had an initial viscosity of about 5000 cps. , but the viscosity increased very rapidly and amounted to just 3 minutes} 10,000 cps. This sample did not have a "workable consistency". The cured samples had the following average hardnesses, as measured on the Rockwell "Black" or C scale: 89.6-3 days; 93.1.- 7 days; 93.5 - 12 days.

This example illustrates the relationship between the amount of water used and the nature of the wet cement pastes, made from normal, untreated cement. This example shows also the effect of reducing the amount of water on the fracture strength properties of the hardened cement pastes (judged according to the hardness values).

Example 2

Cement slurry control samples - conventional addition of additives

a. Lomar D: Two cement paste samples were made as in Example 1 in the first case, 0.6 parts of Lomar D dissolved in 29 parts of water, and in the second case 0.6 parts of Lomar D dissolved in 36.4 parts of water was used. The initial viscosities of the two wet Pastes were about 4,000 cps and 100 cps, respectively. After 5 minutes the viscosity of the first sample had risen to ^ 10,000 cps, and the sample was completely unworkable. The second sample had a viscosity of 7500 cps after 75 minutes on. The cured samples had the following hardness values, measured on the Rockwell C scale: 3 days - (1)

(29 parts water) 91.4; (2) (36.4 parts water) 90.5;

7 days - (1) 96.1, (2) 96.0; 12 days - (1) 97.2, (2) 96.4.

b. Pozzolite: Two cement paste samples were prepared as in Example 2a, with 28 parts of water, the 0.6 g Pozzolite 8 (calcium lignosulfonate based a commercial surcharge for concrete; Master Builders, Cleveland, Ohio), and in the second case 0.6 g of Pozzolite 8 in 35 parts of water were used. The initial viscosity of the two samples were approximately 3000 cps or 1500 cps. After 10 minutes the first sample thickened so much that it was too high for processing consistency. The second sample showed after 75 minutes a viscosity of 8700 cps. The hardened ones Samples had the following hardness values, measured on the Rockwell C scale: 3 days - (1) (28 parts water) 92.7 (2) (35 parts water) 92.3; 7 days - (1) 96.0, (2) 95.4; 12 days - (1) 97.0, (2) 96.1.

This example demonstrates the roughly equal water-reducing activity of Lomar D and Pozzolite 8,

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a commercially available additive that reduces water consumption, detected when both used in a conventional manner, i.e. H. together with the water intended for topping up, be used. Both additives were used in larger amounts than normally prescribed will. Neither of the two additives gave workable consistencies with 28 parts of water. Both practiced a noticeable one retarding effect on the hardening rate, as compared with the degree of hardness increase that of unmodified cements with comparable ones Amounts of water had been applied, was determined.

Example 3 Cement treated with Lomar D.

One lot of Lomar D treated cement was as follows produced: 3 »0 kg of dry type 1 portland cement were placed in a 7> 6 1 Henschel powder mixer. For this 30 g of a 30% strength by weight solution of Lomar D in dimethyl sulfoxide were added (DMSO) given. Immediately after the addition, the mixture was mixed vigorously and thoroughly for 5 minutes. The product was then transferred to a drying dish and heated in a vacuum oven at a reduced pressure of approximately 20 mm Hg at 100 ° C for 2 hours to remove the DMSO to remove. The resulting product was unchanged in appearance compared to the original cement powder.

Using this treated cement that is now about Containing 0.30% adsorbed Lomar D, a series of cement pastes were made by increasing the amount of make-up water and additional free Lomar D dissolved in the water was varied. The compositions and hardness values of the resulting hardened pastes are in Table I compiled. The changes in viscosity

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IH

the samples over time were also determined and are shown graphically in FIG.

Table I.

Parts
Lomar D
on the
cement Treated with Lomar D. Parts
water cement 88.9 91.3. sample
No. 0.30 Parts
Lomar D
in what
ser 42 90.9 93.1 1 0.23 O 40 - hardness (average)
3 days 7 days 12 days 96.7 97.2 2 0.30 O 28 85.5 96.9 96.7 3 0.30 O 28 89.4 96.6 96.2 4th 0.30 0.10 28 95.7 96.2 96.2 5 0.30 0.20 28 95.7 6th 0.30 95.4 96.0

The table and FIG. 1 prove that treated cement (Lomar D adsorbs on the surface of the cement particles) water requirement reducing activity but that the combination of cement treated with Lomar D with free -Lomar D in the top-up water requires very little water, and much less than if Lomar D were used alone in the traditional way (cf. Example 2a (1)) is used. By using the combination of treated and free Lomar D, cement pastes, that have workable consistencies are obtained with just 28 parts of water.

The 3-day hardness values are also important. The; 3-day hardness values of the samples obtained from treated • Cement and 28 parts of water that have been produced are noticeably higher than those of samples of the same composition, in which the chemical additive has only been used in a conventional manner (cf. Example 2). This fact proves the accelerated hardening quality of the treated cement.

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Example 4-

Treated cement - effect of the amount of Lomar D

To assess the effect of showing in varying degrees at the 2 _e ment Upper-r · surface adsorbed Lomar D, a number of Zementbreimassen was prepared which differed only in the amount of adsorbed Lomar D. In this case, the treated cement samples were prepared by rapidly and thoroughly mixing a mixture of 100 parts dry Portland cement Type 1 and varying amounts of 30% Lomar D aqueous solution under low shear conditions in a Waring blender. The samples were allowed to age for at least 24 hours prior to use; no effort was made to remove the added water. There was no difference in appearance between the treated and untreated cement. As a control, two samples in which the Lomar D was only present in the free form were included in the tests.

Cement pastes were made from the samples by thoroughly mixing in the prescribed amount of make-up water, which the designated Amounts of free Lomar D contained. The compositions of these samples and the hardness of themselves resulting hardened pastes are given in Table II. Changing the viscosity of the wet pulp samples with time was also measured and is shown in the figure.

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water hardness
3 days 7 (Average)
Days 12 days 95.7 Parts
Lomar D
on
cement ι 1 le II 28 95.1 96.0 96.4 0.06 the amount of Lomar D on treated cement 28 94.9 96.0 96.3 sample
No. 0.15 Parts
Lomar D
in what
ser 28 95.1 95.7 96.2 1 0.225 0.43 28 95.1 95.7 94.2 2 0.30 0.43 36 91.9 94.1 92.9 3 0 0.43 41.5 90.1 91.3 4th 0 0.43 5 0.6 6th 0.6

The results show that the amount of on the element particles adsorbed Lomar D has a pronounced effect on the consistency of cement pastes, made with constant amounts of water and free Lomar D. The more Lomar D is adsorbed, the lower the viscosity and vice versa. These results also show that the combination of adsorbed Lomar D together with free Lomar D, which is dissolved in the top-up water, is much more effective for achieving a reduction in water requirements and an improved consistency than if simply free Lomar D is used (cf. Examples 1 to 4 with 5 and 6).

This experiment also provides evidence of the accelerated cure rates of Lomar D treated Cement. According to the assessment on the basis of the hardness values, the treated cements achieved about 99% of the 12-day hardness in only 3 days, while comparable, untreated samples showed only about 94% (see Example 2).

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Example 5

Treated Cement - Comparison of the effectiveness of other surfactants and dispersants

Three sets of treated cement samples were prepared to assess the relative activity of other surfactants Agent and dispersant compared to Lomar D. to determine.

a. The first set of samples was in the Waring blender using, in each case, 200 g Portland cement type 1 and 2.0 g 30% aqueous solutions of the various test materials. Each sample was thorough under low shear conditions mixed up, and then left for at least 24 hours harden long before use. The treated cement samples were then washed with 56 g water containing 0.86 g Lomar D, mixed. The compositions are given in Table III, and the viscosity versus time relationships for the wet pastes are indicated in FIG.

b. A second series was similarly made using a 7 »6 1 Patterson-Kelley" V "mixer of the liquid-solid type in place of the Waring mixer and a level of treatment of the cement surface of 0.2 %. instead of 0.30 % . Because of the limited water-reducing power of several of the additives, additional water was added, if necessary, to adjust the initial viscosities to approximately the same level. All samples were used along with 0.4-3% free Lomar D in the make-up water. The compositions of these samples and the hardness of the resulting cured pastes are given in Table IV. The viscosity versus time relationships of the wet pastes are given in FIG.

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c. The third row was set up in the same way as the second row (Patterson-Kelley mixer). The level of treatment of the cement surface was also 0.23% in all cases with the exception of sample No. 29 (0.15 % Lomar D). All treatment chemicals were applied from 30% aqueous solutions including a control which was water only, with the exception of a Lomar D sample applied from DMSO (No. 30). These robes were then all mixed with invariable 40 parts of water that did not contain free Lomar D or other additives. The compositions are given in Table Y and the viscosity versus time relationship of the wet pastes in FIG.

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Table III

Relative Efficacy of Dispersants, Row 1

Sample additional composition 'no. Substance

supplier

2 3 5 ι 6th vD 7th I. 8th σ 9 CD OO . £ -
O 10 * >> 11 O cn 12th tr.

Lomar D CH _? 0-condensed naphthalene sulfonate, sodium salt; ·· Molecular weight 1700

Tamol N CHgO-condensed naphthalene sulfate, sodium salt Daxad 11G Polymerized alkyl naphthalene sulfonate, sodium salt Blancol N CEUO-condensed naphthalene sulfonate, sodium salt Darvan No. 1 CH ₂ 0 ~ condensed naphthalene sulfonate, sodium salt

Petro 250 complex dimethylnaphthalene sulfonate, sodium salt Aerosol OS isopropyl naphthalene sulfonate, sodium salt

Alkanol S tetrahydronaphthalene sulfonate, sodium salt Tanasol D condensed naphthalene sulfonates, sodium salt

Pozzolite 8 lignosulfonate, calcium salt Orzan A lignin sulfonate, ammonium salt

Orzan S lignin sulfonate, sodium salt Nopco Chemical Div. Diamond shamrock

Rohm & Haas Co VR Grace & Co. GAI ¹ Corp.

Vanderbilt Chemical Corp.

Petrochemicals, Co. Ing.

American Cyanamid Co.,

DuPont £ j>

Nopco Chemical Div. Diamond shamrock

Master Builders

Crown Zellerbdch Corp. ιό

Crown Zeller ^ ach Corp. - ^

CO

cn

ISJ

Table IT

Relative Efficacy of Dispersants, Row 2

Sample Zueatz no. material

composition

supplier

14th

15th

16

17 18

19th

20 21 22 23

Lomar D

Lomar PV

Lomar NCO

Of which no.

Blancol

Tamol N

Daxad 11G

Triton X-200

Triton N-57

Katapol PN

Soromin CAZ-75

CHpO-condensed naphthalene sulfonate, Sodium salt, molecular weight 1,700

CHpO-condensed naphthalene suffonate, Sodium salt, molecular weight

CHpO-condensed naphthalene sulfonate, Sodium salt; free acid; Molecular weight 700

CHpO-condenses naphthalene suffonate, Sodium salt

CHpO-condensed naphthalene sulf onate, sodium salt

CHpO-condensed naphthalene suff onate, sodium salt

Polymerized alkyl naphthalene sulfonate, Sodium salt

Sulphated polyoxyethylene alkylphenol, sodium salt

Alkylaryl polyether alcohol polyoxyethylated alkylamine

Complex cationic plasticizer

Nopco Chemical Div. Diamond shamrock

Nopco Chemical Div. Diamond shamrock

Nopco Chemical Div. Diamond shamrock

Vanderbilt Chemical Corp.

GAF Corp. Rohm & Haas

W.R. Grace & Co. Rohm & Haas.

Rohm & Haas GAF Corp. GAF Corp.

To the
cement
adsorbed amount, %

0.23 0.23 0.23 0.23

0.23 0.23

0.23 0.23 0.23 0.23 0.23

Lomar D amount in water, %

0.43

0.43 0.43 0.43

0.43 0.43

0.43 0.43

0.43 0.43 0.43

Water, parts

29 29 29 29

29 29

29

34

33 ro

41! So

CO

Table IV (continued) Relative Effectiveness of Dispersants, Row 2

Sample additional composition fuel

24 Aerosol sodium di- (2'-ethylhexyl) -OT lit

25th OT sulfo succxnate ♦ ^
O N / A Sodium salt of oleic acid <o 26th 01 eat CO Igepal Nonylphenoxypoly- O CA630 (ethylene oxide; O cn cn

supplier Co. To the
cement
adsorbed
Amount, % Lomar D-
Amount in ■
Water, % Water,
Parts VM American
Cyanamide Co. 0.23 0.43 55 4th
U
« American
Cyanamide 0.23 O ,, 43 59 GAF Corp. 0.23 0.45 57 N5 412352

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Table V

Relative effectiveness of dispersants,

line

Sample additional Kr. material

Composition supplier

see sample ETr. 2

see sample Mr. 1

see sample no. 1

see sample Fr. 1

see sample Mr.

see sample no.

see sample no.

see sample no.21

see sample no.6

see sample no.

* Deposited on DMSO

The results of these three series of tests show that the naphthalene sulfonates as a class as an agent for treating the Cement surface are active. When adsorbed on the surface of dry cement, all of them were naphthalene sulfonate compounds with the exception of Petro 250, significantly more effective in reducing water consumption and Control the consistency of wet cement pastes than that

27 Tamol N 28 Lomar D 29 Lomar D 30th Lomar D * 31 water 32 Catapol
PN4-3O 33 Triton
X-200 34 Soromine
CAZ75 35 Sodium-
oleat 36 Triton
N-57 37 Petro
250 38 Aerosol
OT

To the
cement
adsor
biert
Lot,
% Water, ·
Parts 0.23 40 0.23 40 0.15 40 0.23 40 - 40 0.23 40 0.23 40 0.23 40 0.23 40 0.23 40 0.23 40 0.23 40

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other compounds tested. No other compound tested had comparable activity.

As the values show, the surface adsorbed are naphthalene sulfonates active, but their activity is greatly increased if they are used together with free naphthalene sulfonates (Lomar D) or other conventional ones that reduce water requirements Additives such as Pozzolite-8 (see Example 7) j used will.

The compounds tested in this study were representative samples of anionic, cationic and non-ionic dispersants and include three samples of lignosulfonates, the most common being the consistency of wet cement modifiers.

The entire surface treatment was carried out with aqueous solutions, with the exception of sample 30, the Lomar D, the deposited from DMSO.

As from sample Mr. 31 (surface treatment only with As can be seen, water alone is apparently almost almost the sole treatment agent for the surface of dry cement as active as naphthalenesulfonates in reducing the water requirements of cement pastes. However, this sample had a very poor consistency (it settled quickly), and the breaking strength properties were no different than that of normal cement mixed with the same amount of water. The hardness values were after 28 days for comparison: control (40 parts of water) - 95 * 4- ;. with water treated cement, samples Nos. 31-95 »4; treated with Lomar D. Cement, sample No. 28 - 98.3.

One of the series of treated cements in this set of examples was in a Waring mixer, the other two Rows made in a Patterson-Kelley mixer.

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The results are in agreement with one another and indicate "that the effect of the mixing apparatus is comparable.

Example 6 Effect of grinding on cement treated with Lomar D.

A 2 kg batch of Type 1 Portland cement was treated with 20 ml of 30% aqueous Lomar D for 5 minutes in a 7 »6 1 Patterson-Kelley mixer. The resulting treated Zepent was allowed to cure for 24 hours at room temperature. A portion of this material was then ground in a ball mill for 20 hours. At the same time, a batch of untreated cement was also similarly ground for the same period of time and served as a control sample. A 200 g portion of this ground, untreated cement was then treated with 2 ml of 30% aqueous Lomar D in a Waring blender under low shear conditions and the sample allowed to "age" overnight prior to use. The Lomax D content of the sample was 0.3%. Then, from these four samples and the original, unmilled, untreated cement - a total of five samples were made cement pastes: 1) Untreated, unground; 2) untreated, ground; 3) treated (0.3% Lomar D) ₁ ground; 4) ground then treated (0.3% Lomar D); and 5) treated (0.3% Lomar D), unground. In all cases 29 parts of water containing 0.30 parts of free Lomar D were used. As an additional control sample, a pulp sample (sample 6) was prepared in which untreated cement, ground in a ball mill, was mixed with 29 parts of water containing 0.60 parts of free Lomar D. The results are shown in FIG. 6.

The results clearly show that grinding Lomar D treated cement negates the effects of the treatment. The ground, treated cement is despite the 0.30 % Lomar D,

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which it contains, no more active than untreated cement. It it can be predicted that milling will increase the Blaine value and the relative effectiveness of a given amount of Lomar D because of the increased specific surface area of the cement decreases (cf. curves 4 and 5) · -A-Is special sequence of this, the Blaine value of the cement base powder must be taken into account when determining the optimal amount of Lomar D. will.

Example 7

Lomar D-treated cement - effect of free dispersant

A batch of cement containing 0.15% Lomar D (from a 30 *, aqueous solution deposited) was surface-treated, as described in Example 6, in the Patterson-Kelley mixer manufactured. Then two cement slurry samples were prepared by adding 100 parts treated cement and 28 parts Water used in one lalle 0.43 parts free Lomar D and 0.43 parts Pozzolite 8 in the other. The viscosity-time-relationships were established for the wet pastes are determined and are shown graphically in FIG.

The results show that Lomar D-treated cement combined with either the more free Lomar D or Pozzolite 8 in which make-up water is used, results in workable consistencies with only 28 parts of water. Under the conditions In this test, the free Lomar D was somewhat more effective than the free Pozzolite 8. Based on this finding, it can be assumed that that Lomar uses D-treated cement along with conventional cement additives for predictable results can be.

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³⁴¹ 301

Example 8

Lomar D-treated cement - effects of aging

A batch of cement, the surface of which had been treated with 0.15% Lomar D (deposited from a 30% strength aqueous solution), was produced as described in Example 6 in the Patterson-Kelley mixer. Then cement paste samples were prepared after aging periods of 5 minutes, 15 minutes, 1 hour and 24 hours using 28 parts of water which contained 0.4-3 parts of free Lomar D dissolved. As a control, a cement paste was also prepared from a sample of the untreated cement, in which case 0.58 parts of dissolved, free Lomar D were used in the 28 parts of make-up water. (The same amount of Lomar D was thus used in all cases.) The viscosity-versus-time relationships are shown in FIG. 8 (samples A to E). FIG. 8 also shows the viscosity-versus-time relationships of cement pastes which were prepared from a cement sample treated with 0.23% Lomar D and aged for 24 hours and 115 days (samples F and G ).

The results show that Lomar D applied in aqueous solution has an aging time that is longer than about 5 minutes, required to impart the unusual properties of the present invention. Preserves optimal properties one after aging for 15 minutes or more. Expansive Aging times do not change the properties of the treated cement.

Example 9 Foamed concrete

The effectiveness of cement treated with Lomar D on the freeze-thaw resistance of foamed lightweight concrete

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341 301 Λ \

was determined in a series of four experiments ". Two masses were made from treated cement and two controls made from untreated cement used ground sand made by ball milling conventional sand for 8 hours. Two of the samples - one with treated cement, the other without also some baked plaster (Plaster of Paris). The masses were made as follows: 400 parts ground sand was mixed with 120 parts of hot water. 100 parts of the cement and optionally 3 parts of plaster of paris were then added to the wet sand mixture and stirred until a uniform consistency was achieved. Additionally hot water was added if necessary to achieve a stirrable consistency. Next were in one special process 0.43 parts aluminum powder with 45 parts mixed with hot water and stirred thoroughly until homogeneous. This mixture was then quickly with the wet cement (gypsum) and the sand slurry mixed together. After thorough mixing, the warm, wet pulp became into a Cast shape with straight walls. The foam is almost starting to climb instantly and reach its maximum height after about 2 hours. The samples are then placed in a steam autoclave brought, and the pressure is gradually increased so that a water vapor temperature of about 190 C results, where the samples are held for about 16 hours. The densities of the resulting foams were 0.7-0.8 g / cm3.

The freeze-thaw resistance of the foamed concrete samples was determined in the following way: 2.5 x 2.5 x 7 »5 cm large test blocks were cut out of the foamed cake. These sample blocks were immersed in a pan of water until saturated. The pan and its contents were then placed in a freezer and frozen solid. After 16 hours, the pan and its contents were out of the freezer taken out and allowed to thaw the contents for 8 hours. This way of working has been repeated several times.

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341 301

get. The samples were examined after each cycle to To determine the degree of damage caused by freezing and thawing was caused.

The compositions of the samples and the results of the freeze-thaw test are shown in Table VI.

Table VI

Foamed concrete: compositions and freeze-thaw stability

lity

Sample ur.

Compositions (, parts by weight Untreated cement with 0.15% Lomar D-

100

100

treated cement - Little
Chipping 100 100 - Ground sand 400 Completely
ge Destroy
tion of the
surface 400 400 400 Aluminum powder 0.45 0.45 0.45 0.45 Hot water 170 170 170 170 Ground plaster - - 3 3 Freeze-thaw resistance 5 cycles No
Change
change No
Change
change Completely
dige zer
disturbance
the waiter
area 16 cycles Partially
se zer
disturbance
the waiter
area No
Change
change -

The results show that from cement treated with Lomar D. foamed concrete samples produced a much better freeze-thaw resistance than foams made from conventional cement.

409840/0755

Claims (12)

Patent claims eh e M.i method to improve plasticity in the open V / storage of a hydraulic cement mass, characterized in that that you can get into dusty, hydraulic cement without significantly increasing its specific surface area According to Blaine, evenly mixes in a solution that is effective and increases the plasticity in open storage Contains amount of an additive which is a condensed kaphthalenesulfonic acid, a sulfonate or a sulfonic acid derivative comprises, the amount of the solution being insufficient for the dusty appearance of the aforesaid To change cement significantly, and to age the resulting mass for at least 15 minutes. 2. The method according to claim 1, characterized in that the cement is Portland cement. 3. The method according to claim 1 or 2, characterized in that the cement has a Blaine specific surface area of about 2500 to about 4000 cm ² / g before the solution is mixed. 4. The method according to any one of claims 1 to 3> characterized in that that the solution is an aqueous solution consisting essentially of about 0.03 to about 0.5% of the additive and consists of about 0.1 to about 1.5 percent water, both based on the weight of the dry cement. 5. The method according to any one of claims 1 to 4, characterized in that that the additive is a formaldehyde condensed naphthalene sulfonate with a degree of condensation is greater than 3. - 29 409840/0755 341 501 * OK 6. The method according to any one of claims 1 to 5> characterized in that the additive is an alkali metal salt a naphthalenesulfonic acid condensed with formaldehyde with a degree of condensation of about 7. 7- method according to one of claims 1 "to 6, characterized in that that the. Cement is a type 1 portland cement. 8. Composition containing hydraulic cement with increased plasticity in open storage, produced by evenly mixing in dusty, hydraulic cement a solution containing an effective amount of condensed plastic that increases open storage plasticity Naphthalene additive, namely a condensed naphthalene sulfonic acid, a sulfonate or a sulfonic acid derivative, contains, the amount of the solution being insufficient to the dusty nature of the cement adversely, and by aging the resulting mass for at least 15 minutes. 9 · mass according to claim 8, characterized in that the Cement is a cement according to one of claims 2, 3 or 7. 10. Composition according to claim 8 or 9 »characterized in that that the solution consists essentially of about 0.05 to about 0.3% of the additive and of about 0.10 to about 1.5% Water, both based on the weight of the dry cement. 11. Composition according to one of claims 8 to 10, characterized in that that the additive is an additive according to claim 5 or 6. - 30 409840/0755 34-1 301 12. Treated, dusty cement containing a dusty cement, which is in dusty form with an additive, namely condensed naphthalenesulfonic acids, Salts and other acid derivatives as salts, "has been treated. - 31 409840/0755