Cement compositions.

0001The invention relates to cement compositions and to additives for use in such compositions which improve the air entrainment properties during manufacture. In particular, the invention relates to cement compositions containing pulverised fuel ash which contains carbon as a component.

0002Cement compositions with which the invention is concerned includes concretes which comprise cement aggregate, sand and water; mortars which comprise cement, sand and water; lime sand and water or mixtures containing both lime and cement. High pressure steam cured concretes comprising cement aggregate and water, lime or limestone and siliceous materials such as silica flour and water are also included. The improved physical characteristics produced in cement compositions prepared according to this invention result from air entrainment. The entraining of air in such compositions is known to improve durability of concretes, particularly resistance to frost damage and also improve the flow characteristics, which are of importance for cement pumping and other concrete placing operations. The working characteristics of mortars are also improved by entraining a proportion of air which can reduce the proportion of lime required in the composition.

0003It has been proposed to utilise pulverised fuel ash, also referred to as flyash, as a component in concretes and the requirements for such a component are given in British Standard 3892 (Part 1) 1982, however the present invention is not limited to the fuel ashes described in this standard. The pulverised fuel ash, as it will be termed in this specification, is the ash residue from pulverised fuel. The Applicants have found the presence of carbon in the fuel ash reduces the ability of air entraining agents to operate effectively.

0004GB-A-1434924 discloses a cement composition containing pulverised fuel ash and C8 to C10 fatty acids in order to improve the water absorption of a cement.

0005Thus the present invention describes cement compositions having a proportion of pulverised fuel ash as a component, usually up to about 65% and having a loss on ignition up to about 12%, with an air entrainment agent which is effective despite the presence of the carbon.

0006The invention provides a cement composition containing up to about 65% of pulverised fuel ash and an air entrainment agent together with an amount of a water soluble C₈ fatty acid salt effective to negate the surface activity of the carbon content of the fuel ash. The C8 fatty acid salt is preferentially absorbed on the carbon surface thus allowing the air entrainment agent to remain free in the composition. Usually the fatty acid salt used will be the sodium or potassium salt but the invention contemplates having an additive, the fatty acid, added to the cement composition which reacts with other components of the composition to generate the desired fatty acid salts in situ. The upper level of C8 fatty acid salt added is usually determined by economic factors but it is usually not above about 0.1%, more usually not above 0.05% w/w on the amount of cement.

0007The air entrainment agent is preferably the water soluble C9 and C10 fatty acid salts described in GB 1435301 (Unilever); these are added preferably in an amount of 0.005 to 0.1% by weight of the active binder i.e. cement in the formulation. The active binder is the cement in a cementiferous composition and/or the calcium silicate produced by reaction of lime or limestone with siliceous materials in the compositions. Other air entrainment agents are usable with the octanoate salt of the present invention. Examples of these agents are salts of vinsol resins (abietic acid salts) ether sulphates, alkyl sulphonates, alkyl aryl sulphonates, salts of fatty acids and amine oxide salts.

0008The additive defined above provides air entrainment which is stable over a period and effective for pulverised fuel ashes having a range of loss on ignition (LOI) values. The latter values measure the loss of water and other volatiles, and in particular carbon, at elevated temperatures. The water soluble C8 fatty acid salts are effective with LOI of from about 1.5% to about 6% by weight.

0009Suitable fatty acid fractions for use in this invention may be obtained as by product fractions from the distillation of vegetable oils, for example coconut or ground nut oils, which contain a proportion of the desired chain length acids.

0010The following experiments illustrate the benefit achieved with the use of the cement additive of the invention.

0011A cementitious composition comprising:- <tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">Kg/m³</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Ordinary Portland Cement</entry><entry namest="col2" nameend="col2" align="right">200</entry></row><row><entry namest="col1" nameend="col1" align="left">Pulverised Fuel Ash</entry><entry namest="col2" nameend="col2" align="right">100</entry></row><row><entry namest="col1" nameend="col1" align="left">Almington Pit Sand (Grade M)</entry><entry namest="col2" nameend="col2" align="right">600</entry></row><row><entry namest="col1" nameend="col1" align="left">Croxden 20 mm's, Gravel</entry><entry namest="col2" nameend="col2" align="right">850</entry></row><row><entry namest="col1" nameend="col1" align="left">Croxden 10 mm's, Gravel</entry><entry namest="col2" nameend="col2" align="right">375</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Free Water</entry><entry namest="col2" nameend="col2" align="right">175</entry></row></tbody></tgroup></table></tables>

0012The composition was formed into concrete using the procedure described in British Standard 5075.

0013The additive comprised 6% of sodium octanoate and 8% sodium decanoate in aqueous solution. The performance of the additive was compared with that of a solution of 14% sodium vinsolate, a material widely used in this application. The air content was measured by the method given in British Standard 5075. That is four sets of experiments were conducted using pulverised fuel ashes with varying levels of carbon content (loss on ignition).

0014For each set of experiments both the additive and sodium vinsolate were used to produce air entrained concretes. The stability of the air in the concrete was then measured before and after vigorous mixing. The objective was to introduce an air entrainment of about 6% V/V.

0015In all cases, the air void system produced by the additive was markedly superior to that produced by sodium vinsolate in that the retained air was more stable and thus the rate of air loss was lower with the additive of the invention. The additive was dosed as mls per 50 Kg cement.

EXPERIMENT 1

0016<tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="6" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="26.25mm" /><colspec colnum="2" colname="col2" colwidth="26.25mm" /><colspec colnum="3" colname="col3" colwidth="26.25mm" /><colspec colnum="4" colname="col4" colwidth="26.25mm" /><colspec colnum="5" colname="col5" colwidth="26.25mm" /><colspec colnum="6" colname="col6" colwidth="26.25mm" /><thead valign="top"><row><entry namest="col1" nameend="col6" align="left">PULVERISED FUEL ASH, SOURCE 1</entry></row><row><entry namest="col1" nameend="col1" align="center">NOMINAL L.O.I</entry><entry namest="col2" nameend="col2" align="left">ADMIXTURE</entry><entry namest="col3" nameend="col3" align="center">DOSE (mls/50 Kg)</entry><entry namest="col4" nameend="col6" align="center">AIR CONTENT (% V.V)</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" align="center">INITIAL</entry><entry namest="col5" nameend="col6" align="center">ADDITIONAL MIXING</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" align="center">2 MINS MIXING</entry><entry namest="col6" nameend="col6" align="center">4 MINS MIXING</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Low</entry><entry namest="col2" nameend="col2" align="left">The additive</entry><entry namest="col3" nameend="col3" align="right">100</entry><entry namest="col4" nameend="col4" align="char" char=".">7.5</entry><entry namest="col5" nameend="col5" align="char" char=".">7.5</entry><entry namest="col6" nameend="col6" align="char" char=".">7.3</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Low</entry><entry namest="col2" nameend="col2" align="left">Vinsol Resin Type</entry><entry namest="col3" nameend="col3" align="right">80</entry><entry namest="col4" nameend="col4" align="char" char=".">5.6</entry><entry namest="col5" nameend="col5" align="char" char=".">4.7</entry><entry namest="col6" nameend="col6" align="char" char=".">3.9</entry></row></tbody></tgroup></table></tables>

EXPERIMENT 2

0017<tables id="tabl0003" num="0003"><table frame="all"><tgroup cols="6" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="26.25mm" /><colspec colnum="2" colname="col2" colwidth="26.25mm" /><colspec colnum="3" colname="col3" colwidth="26.25mm" /><colspec colnum="4" colname="col4" colwidth="26.25mm" /><colspec colnum="5" colname="col5" colwidth="26.25mm" /><colspec colnum="6" colname="col6" colwidth="26.25mm" /><thead valign="top"><row><entry namest="col1" nameend="col6" align="left">PULVERISED FUEL ASH, SOURCE 2</entry></row><row><entry namest="col1" nameend="col1" align="center">NOMINAL L.O.I</entry><entry namest="col2" nameend="col2" align="left">ADMIXTURE</entry><entry namest="col3" nameend="col3" align="center">DOSE (mls/50 Kg)</entry><entry namest="col4" nameend="col6" align="center">AIR CONTENT (% V.V)</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" align="center">INITIAL</entry><entry namest="col5" nameend="col6" align="center">ADDITIONAL MIXING</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" align="center">2 MINS MIXING</entry><entry namest="col6" nameend="col6" align="center">4 MINS MIXING</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Medium</entry><entry namest="col2" nameend="col2" align="left">The additive</entry><entry namest="col3" nameend="col3" align="right">50</entry><entry namest="col4" nameend="col4" align="char" char=".">6.0</entry><entry namest="col5" nameend="col5" align="char" char=".">6.0</entry><entry namest="col6" nameend="col6" align="char" char=".">6.0</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Medium</entry><entry namest="col2" nameend="col2" align="left">Vinsol Resin Type</entry><entry namest="col3" nameend="col3" align="right">40</entry><entry namest="col4" nameend="col4" align="char" char=".">6.0</entry><entry namest="col5" nameend="col5" align="char" char=".">4.5</entry><entry namest="col6" nameend="col6" align="char" char=".">3.6</entry></row></tbody></tgroup></table></tables>

EXPERIMENT 3

0018<tables id="tabl0004" num="0004"><table frame="all"><tgroup cols="6" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="26.25mm" /><colspec colnum="2" colname="col2" colwidth="26.25mm" /><colspec colnum="3" colname="col3" colwidth="26.25mm" /><colspec colnum="4" colname="col4" colwidth="26.25mm" /><colspec colnum="5" colname="col5" colwidth="26.25mm" /><colspec colnum="6" colname="col6" colwidth="26.25mm" /><thead valign="top"><row><entry namest="col1" nameend="col6" align="left">PULVERISED FUEL ASH, SOURCE 3</entry></row><row><entry namest="col1" nameend="col1" align="center">NOMINAL L.O.I</entry><entry namest="col2" nameend="col2" align="left">ADMIXTURE</entry><entry namest="col3" nameend="col3" align="center">DOSE (mls/50 Kg)</entry><entry namest="col4" nameend="col6" align="center">AIR CONTENT (% V.V)</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" align="center">INITIAL</entry><entry namest="col5" nameend="col6" align="center">ADDITIONAL MIXING</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" align="center">2 MINS MIXING</entry><entry namest="col6" nameend="col6" align="center">4 MINS MIXING</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">High</entry><entry namest="col2" nameend="col2" align="left">The additive</entry><entry namest="col3" nameend="col3" align="right">100</entry><entry namest="col4" nameend="col4" align="char" char=".">7.5</entry><entry namest="col5" nameend="col5" align="char" char=".">7.6</entry><entry namest="col6" nameend="col6" align="char" char=".">7.3</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">High</entry><entry namest="col2" nameend="col2" align="left">Vinsol Resin Type</entry><entry namest="col3" nameend="col3" align="right">100</entry><entry namest="col4" nameend="col4" align="char" char=".">6.6</entry><entry namest="col5" nameend="col5" align="char" char=".">4.6</entry><entry namest="col6" nameend="col6" align="char" char=".">3.7</entry></row></tbody></tgroup></table></tables>

EXPERIMENT 4

0019<tables id="tabl0005" num="0005"><table frame="all"><tgroup cols="6" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="26.25mm" /><colspec colnum="2" colname="col2" colwidth="26.25mm" /><colspec colnum="3" colname="col3" colwidth="26.25mm" /><colspec colnum="4" colname="col4" colwidth="26.25mm" /><colspec colnum="5" colname="col5" colwidth="26.25mm" /><colspec colnum="6" colname="col6" colwidth="26.25mm" /><thead valign="top"><row><entry namest="col1" nameend="col6" align="left">PULVERISED FUEL ASH, SOURCE 4</entry></row><row><entry namest="col1" nameend="col1" align="center">NOMINAL L.O.I</entry><entry namest="col2" nameend="col2" align="left">ADMIXTURE</entry><entry namest="col3" nameend="col3" align="center">DOSE (mls/50 Kg)</entry><entry namest="col4" nameend="col6" align="center">AIR CONTENT (% V.V)</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" align="center">INITIAL</entry><entry namest="col5" nameend="col6" align="center">ADDITIONAL MIXING</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" align="center">2 MINS MIXING</entry><entry namest="col6" nameend="col6" align="center">4 MINS MIXING</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">High</entry><entry namest="col2" nameend="col2" align="left">The additive</entry><entry namest="col3" nameend="col3" align="right">250</entry><entry namest="col4" nameend="col4" align="char" char=".">6.8</entry><entry namest="col5" nameend="col5" align="char" char=".">6.2</entry><entry namest="col6" nameend="col6" align="char" char=".">6.1</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">High</entry><entry namest="col2" nameend="col2" align="left">Vinsol Resin Type</entry><entry namest="col3" nameend="col3" align="right">200</entry><entry namest="col4" nameend="col4" align="char" char=".">6.1</entry><entry namest="col5" nameend="col5" align="char" char=".">2.8</entry><entry namest="col6" nameend="col6" align="char" char=".">1.7</entry></row></tbody></tgroup></table></tables>

EXPERIMENT 5

0020A cement additive composition prepared from: <tables id="tabl0006" num="0006"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">C8/C10 fatty acids (60/40%w/w)</entry><entry namest="col2" nameend="col2" align="left">15% bywt</entry></row><row><entry namest="col1" nameend="col1" align="left">Sodium hydroxide solution (100°Tw)</entry><entry namest="col2" nameend="col2" align="left">8.5%</entry></row><row><entry namest="col1" nameend="col1" align="left">Tetralon A (a surfactant)*</entry><entry namest="col2" nameend="col2" align="left">1.0%</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Water</entry><entry namest="col2" nameend="col2" align="left">Remainder</entry></row></tbody></tgroup><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col2" align="justify">* was obtained from Allied Colloids of Low Moor, Bradford, England.</entry></row></tbody></tgroup></table></tables> was tested for air entrainment using a pulverised fuel ash containing 5.7% carbon (LO1). This additive composition gave 4.7% air entrainment while the use of 6% C8 fatty acid and 6% C10 fatty acid (i.e. 12% w/w of a 50:50 mixture) gave 3.4% air entrainment. Thus the benefit of using C8 fatty acid salt is clearly demonstrated. The C8 fatty acid alone gave no air entrainment and the C10 acid alone gave a value (2.0%) below that required by the British Standard (4.5 ± 1.5%)