CA1229629A - Additive of protein nature for hydraulic cements, mortars and concretes, and use thereof in the field of construction - Google Patents
Additive of protein nature for hydraulic cements, mortars and concretes, and use thereof in the field of constructionInfo
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- CA1229629A CA1229629A CA000462998A CA462998A CA1229629A CA 1229629 A CA1229629 A CA 1229629A CA 000462998 A CA000462998 A CA 000462998A CA 462998 A CA462998 A CA 462998A CA 1229629 A CA1229629 A CA 1229629A
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Abstract
Additive of protein nature for hydraulic cements, mortars and concretes, and use thereof in the field of construction ABSTRACT OF THE DISCLOSURE
The present invention relates to a novel additive for hydraulic cements, mortars and concretes, particularly for improving the mechanical strengths and the workability and for reducing sweating and segregation, which is characterized in that it is a protein hydrolysate having a pH
less than or equal to 6, comprising substances selected from the group constituted by proteins, polypeptides, aminoacids and mixtures thereof, and obtained by treating 100 volumes of an aqueous composition contai-ning at least one protein substance selected from the group constituted by proteins, polypeptides and mixtures thereof, with at least one bacterial strain producing lactic acid having a population greater than or equal to 102 germs/cm3, in the presence of 0.5 to 30 parts by weight of a source of carbon belonging to the family of carbohydrates, for at least 2 hours, at a temperature of between 0 and 65°C and at a pH less than or equal to 6.
The present invention relates to a novel additive for hydraulic cements, mortars and concretes, particularly for improving the mechanical strengths and the workability and for reducing sweating and segregation, which is characterized in that it is a protein hydrolysate having a pH
less than or equal to 6, comprising substances selected from the group constituted by proteins, polypeptides, aminoacids and mixtures thereof, and obtained by treating 100 volumes of an aqueous composition contai-ning at least one protein substance selected from the group constituted by proteins, polypeptides and mixtures thereof, with at least one bacterial strain producing lactic acid having a population greater than or equal to 102 germs/cm3, in the presence of 0.5 to 30 parts by weight of a source of carbon belonging to the family of carbohydrates, for at least 2 hours, at a temperature of between 0 and 65°C and at a pH less than or equal to 6.
Description
- l -The present invention relates to a novel additive of protein nature, for hydraulic cements, mortars and concretes. It also relates to the use of this additive in the field of construction.
The expression "protein substance" or "substance of protein 5 nature" is understood in the following specification to mean any product belonging to the group constituted by proteins, polypeptides and mixtures thereof; and the expression "protein hydrolysate" is understood to mean any product belonging to the group constituted by proteins, polypeptides, amino acids and mixtures thereof.
It has already been recommended to use proteins in the building field, particularly for making cellular concretes and light colloidal con-crepes. According to the indications given in KElTEL's work "Cement:
Hairstyling undo Eigenschaften", Springer-Verlag Berlin-Heidelberg-New York 1971, page 186, lines 38-40, it is thought that the ancient Remans 15 used animal blood in the manufacture of porous concrete. However, the use of proteins raises difficulties in the building field by inducing delays in setting, as indicated by OUZEL in "Adjutant duo ciment'l, Editions Star, Paris 19653 pages 45 and 105.
Furthermore, it is known from US. Patent No. 4 203 674, which 20 recommends using blood in powder form as air-entraining killed in associa-lion with another killed (in particular hydroxyethylcellulose, hydroxy-propylmethylcellulose and carboxymethylcellulose) to obtain lightened concretes and mortars, that liquid blood is not suitable for making said lightened concretes and mortars.
Various aspects of this mention are as follows:
A protein additive for hydraulic cements, mortars and concretes, useful for improving the mechanical properties and the workability and for reducing sweating and segregation, wherein it is a protein hydrolysate having a pi less than or equal to 30 6, comprising substances selected from the group constituted by proteins, polypeptides, amino acids and mixtures thereof, and obtained by treating 100 volumes of an aqueous composition containing at least one protein substance selected from the group constituted by proteins, polypeptides and mixtures thereof, with at least one bacterial strain producing lactic 35 acid having a population greater than or equal to 102 germs/cm3, in the presence of 0.5 to 30 parts by weight of a source of carbon belonging I, .. I, .
-lo-to the family of carbohydrates, for at least 2 hours, at a temperature of between 0 and 65C and at a pi less than or equal to 6.
A protein additive for hydraulic cements, mortars and concretes, useful for improving the mechanical properties and the workability and 5 for reducing sweating and segregation, wherein it is a protein hydrolysate having a pi less than or equal to 6, comprising substances selected from the group constituted by proteins, polypeptides, amino acids and mixtures thereof, and obtained by treating lo volumes of an aqueous composition containing at least one protein substance selected from the group keenest-10 tuned by liquid animal blood to which an anticoagulant is added, thither offal proteins, meat product proteins, whole fish proteins, fish waste proteins and mixtures thereof, with at least one bacterial strain producing lactic acid having a population greater than or equal to lo germs/cm3, in the presence of 0.5 to 30 parts by weight of a source 15 of carbon belonging to the family of carbohydrates, for at least 2 hours, at a temperature of between 0 and 65C and at a pi less than or equal to 6.
A protein additive for hydraulic cements, mortars and concretes, useful for improving the mechanical properties and the workability and 20 for reducing sweating and segregation, wherein it is a protein hydrolysate having a pi less than or equal to 6, comprising substances selected from the group constituted by proteins, polypeptides, amino acids and mixtures thereof, and obtained by treating lo volumes of an aqueous composition containing at least one protein substance constituted by liquid animal 25 blood to which an anticoagulant is added, with at least one bacterial strain producing lactic acid having a population greater than or equal to lo germs/cm3, in the presence of 0.5 to 30 parts by weight of a source of carbon belonging to the family of carbohydrates, for at least
The expression "protein substance" or "substance of protein 5 nature" is understood in the following specification to mean any product belonging to the group constituted by proteins, polypeptides and mixtures thereof; and the expression "protein hydrolysate" is understood to mean any product belonging to the group constituted by proteins, polypeptides, amino acids and mixtures thereof.
It has already been recommended to use proteins in the building field, particularly for making cellular concretes and light colloidal con-crepes. According to the indications given in KElTEL's work "Cement:
Hairstyling undo Eigenschaften", Springer-Verlag Berlin-Heidelberg-New York 1971, page 186, lines 38-40, it is thought that the ancient Remans 15 used animal blood in the manufacture of porous concrete. However, the use of proteins raises difficulties in the building field by inducing delays in setting, as indicated by OUZEL in "Adjutant duo ciment'l, Editions Star, Paris 19653 pages 45 and 105.
Furthermore, it is known from US. Patent No. 4 203 674, which 20 recommends using blood in powder form as air-entraining killed in associa-lion with another killed (in particular hydroxyethylcellulose, hydroxy-propylmethylcellulose and carboxymethylcellulose) to obtain lightened concretes and mortars, that liquid blood is not suitable for making said lightened concretes and mortars.
Various aspects of this mention are as follows:
A protein additive for hydraulic cements, mortars and concretes, useful for improving the mechanical properties and the workability and for reducing sweating and segregation, wherein it is a protein hydrolysate having a pi less than or equal to 30 6, comprising substances selected from the group constituted by proteins, polypeptides, amino acids and mixtures thereof, and obtained by treating 100 volumes of an aqueous composition containing at least one protein substance selected from the group constituted by proteins, polypeptides and mixtures thereof, with at least one bacterial strain producing lactic 35 acid having a population greater than or equal to 102 germs/cm3, in the presence of 0.5 to 30 parts by weight of a source of carbon belonging I, .. I, .
-lo-to the family of carbohydrates, for at least 2 hours, at a temperature of between 0 and 65C and at a pi less than or equal to 6.
A protein additive for hydraulic cements, mortars and concretes, useful for improving the mechanical properties and the workability and 5 for reducing sweating and segregation, wherein it is a protein hydrolysate having a pi less than or equal to 6, comprising substances selected from the group constituted by proteins, polypeptides, amino acids and mixtures thereof, and obtained by treating lo volumes of an aqueous composition containing at least one protein substance selected from the group keenest-10 tuned by liquid animal blood to which an anticoagulant is added, thither offal proteins, meat product proteins, whole fish proteins, fish waste proteins and mixtures thereof, with at least one bacterial strain producing lactic acid having a population greater than or equal to lo germs/cm3, in the presence of 0.5 to 30 parts by weight of a source 15 of carbon belonging to the family of carbohydrates, for at least 2 hours, at a temperature of between 0 and 65C and at a pi less than or equal to 6.
A protein additive for hydraulic cements, mortars and concretes, useful for improving the mechanical properties and the workability and 20 for reducing sweating and segregation, wherein it is a protein hydrolysate having a pi less than or equal to 6, comprising substances selected from the group constituted by proteins, polypeptides, amino acids and mixtures thereof, and obtained by treating lo volumes of an aqueous composition containing at least one protein substance constituted by liquid animal 25 blood to which an anticoagulant is added, with at least one bacterial strain producing lactic acid having a population greater than or equal to lo germs/cm3, in the presence of 0.5 to 30 parts by weight of a source of carbon belonging to the family of carbohydrates, for at least
2 hours, at a temperature of between 0 and 65C and at a pi less than 30 or equal to 6.
The invention recommends a novel technical solution for impure-vying the mechanical strengths (particularly the tensile, bending and come pressive strengths), for reducing sweating and segregation, and finally for improving the workability of the hydraulic cements, concretes and 35 mortars. This novel technical solution which favorably modifies a certain number of theological parameters, employs liquid protein hydrolysates which differ from the additives heretofore known in the building domain.
I I
The protein additive recommended according to the invention for improving the mechanical properties, the workability and for reducing sweating and segregation of the hydraulic cements, concretes and mortars?
is characterized in that it is a protein hydrolysate having a pi less .
than or equal to 6, comprising substances selected from -the group keenest-tuned by proteins, polypeptides, amino acids and mixtures thereof, and obtained by treating 100 parts by weight of an aqueous composition contain nine at least one protein substance selected from the group constituted 5 by proteins, polypeptides and mixtures thereof, with at least one bacterial strain producing lactic acid having a population greater than or equal to 102 germs/cm3, in the presence of 0.5 to 30 parts by weight of a source of carbon belonging to the family of carbohydrates, for at least 2 hours, at a temperature of between 0 and 65C and at a pi less than 10 or equal to 6.
The protein hydrolysate useful according to the invention in the construction domain may be used directly in the liquid or humid state. Before being associated with a hydraulic cement and with water, or as the case may be, with a hydraulic cement, water with sand and/or 15 granulates, it may be conserved in a suitable recipient for at least 18 months at a temperature of between -5 and +60C.
The protein additive according to the invention differs, by the mode by which it is obtained, from the means recommended by German Patent No. 511 513 on the one hand and the summary of Chemical Abe 20 streets 88, 140 835 t, on the other hand.
Among suitable protein hydrolysates, particular mention may be made of those obtained from animal or plant proteins. Among these proteins, mention may be made of proteins of animal origin such as meat product proteins, offal product proteins, milk proteins, whole fish 25 proteins, fish wastes, albumins (particularly egg albumin), and plant proteins such as those contained in the Leguminous, oleaginous plants, Sullenness (particularly tobacco) and algae.
Protein substances which are suitable for obtaining the hydra-Lucite according to the invention are in particular the animal and plant 30 proteins mentioned above as well as the hydrolysates and proteolysates of said animal and plant proteins which comprise, in particular, either proteins which have not yet broken down, or polypeptides, or mixtures of proteins and polypeptides, in association, as the case may be, with amino acids.
The ground meat product proteins or the ground or liquid offal ~2~g~
product proteins are advantageously rapidly subjected to treatment with bacteria producing lactic acid. Before such treatment, especially if it is delayed, it is recommended to associate with the protein substances I to 15% by weight of crushed cereals.
The following bacteria producing lactic acid may be used in the preparation of the hydrolysate useful according to the invention as additive in the construction domain: Streptococcus (particularly Streptococcus bevies Streptococcus thermophilus, Streptococcus focalize S ptococcus faecium, Streptococcus creamers, Streptococcus lactic), 10 Leuconostoc (particularly Leuconostoc mesenteroides, Leuconostoc lactic, Leuconostoc creamers) and Lactobacillus (particularly Lactobacillus delbrueckii, Lactobacillus leichmanii, Lactobacillus jensenii, Lactobacillus lactic, Lactobacillus bul~aricus, Lactobacillus helveticus, Lactobacillus acidophilus, Lactobacillus easel, Lactobacillus planetarium). Among suitable 15 strains, particular mention may be made of the strains of the Collection of -the Pasteur Institute: Streptococcus bevies 56.23~ Streptococcus _hermophilus 66.31~ Streptococcus focalize 54.32~ Streptococcus faecium 54.31~ Streptococcus lactic 70.57, Leuconos-toc mesenteroides aye Lactobacillus delbrueckii 57.8~ Lactobacillus leichmanii 53.61~ 53.3 and 20 53.4, Lactobacillus jensenii 69.17~ Lactobacillus bul~aricus 71.36~ Lookout-bacillus helveticus 57.15~ Lactobacillus acidophilus 76.13 and 71.34 Lactobacillus easel 71.37~ 71.38 and A 158~ Lactobacillus planetarium 71.39~
and the strain of the catalog of the American Type Culture Collection:
Lactobacillus lo ATTICS 8000.
According to the invention, one or more strains of lactic acid-producing bacteria will be used. The bacterial population will be between 102 germs/cm3 and 108 germs/cm3, and advantageously between 103 germs/
cm3 and 106 germs/cm3.
The total content of protein substance and amino acid contained 30 in the liquid protein hydrolysate according to the invention is between 0.5 and 50% weight/volume. If necessary, the protein hydrolysate may be concentrated in vacua and/or sterilized.
The carbohydrates used as source of carbon may be hydrolyzable or non-hydrolyzable, the preferred carbohydrates being in particular 35 glucose, lactose! succors, maltose, water-soluble starch and whey.
~lZ2~6~
It is possible to select the or each bacterial strain which may be used according to the invention by referring on the one hand to the intrinsic stability of the liquid protein hydrolysate obtained and on the other hand to a test of use which may be described as follows:
Two concretes A and B, of the following composition, are made:
A B
- cement of CP5 45 type with fillers 400 g 400 g - lime, type HA 40 g 40 g 10 - light granulate 2 1 2 1 (polystyrene, I to 5 mm diameter) - additive 0 22 g The role of the additive according to the invention added to concrete B will be a densification of said concrete equivalent to at least 10 per cent of entrained air.
According to the invention, a process for manufacturing a con-struction element from a hydraulic cement, water and a liquid protein additive is recommended, wherein 100 parts by weight of hydraulic cement are mixed with 0.001 to 10 parts by weight of liquid protein additive 20 previously diluted with mixing water. 20 to 50 parts by weight of mixing water for 100 parts by weight of hydraulic cement will advantageously be used.
According to this process, sand and/or granulates, which may be light and possibly expanded (polystyrene balls, glass balls, mica, vermin quilt) or heavy depending on the desired density of the construction material, may also be introduced.
Four types of material may be obtained by the process of the invention, namely:
material A, from 30 - 100 parts by weight of hydraulic cement, and - 0.001 to 10 parts by weight of protein additive;
material B, from - 100 parts by weight of hydraulic cement, ~2g~
- 0.001 to 10 parts by weight of protein additive, and - I to 9000 parts by weight of sand;
material C, from - 100 parts by weight of hydraulic cement, - 0.001 to 10 parts by weight of protein additive, and - I to 90000 parts by weight of granulates; and material D, from - 100 parts by weight of hydraulic cement, - 0.001 to 10 parts by weight of protein additive, - I to 9000 parts by weight of sand, and - I to 90000 parts by weight of granulates.
The best embodiment of the invention consists, to obtain a construction material, in mixing 100 parts by weight of hydraulic cement (particularly cement or blast furnace slag) with 0.001 to 10 parts by weight of protein additive previously diluted in, preferably, 30 to 35 parts by weight of water with, as the case may be, sand and/or light or heavy granulates, the protein additive being obtained from liquid animal blood which is one of the elements of offal. The fresh animal blood which is collected at the abutter must have an anti-coagulant added thereto (particularly an anti-coagulant selected from the group constituted by the alkali metal citrates, polyphosphates, heparin and silicones) within the five minutes following bleeding. 0.05 to I part by dry weight of anti-coagulant will advantageously be incorporated with 100 parts by weight of fresh liquid blood, treatment with the bacteria producing lactic acid being carried out at the latest 6 hours after bleeding.
It is unnecessary to employ a particular mixer as indicated in US. Patent No. 4 203 674 mentioned above, the cement is mixed with mixing water containing the protein additive, then, as the case may be, sand and/or granulates, in a conventional mixer operating at 30 50-100 rum.
Other advantages and features of the invention will be more readily understood on reading the following description of embodiments which are in no way limiting but given by way of illustration.
EXAMPLE I
Concrete incorporating hi granulates 6~2~
A concrete is prepared from the following ingredients:
- hydraulic cement 250 parts by weight - sand having particles with a diameter smaller than or equal to 0.8 mm 50 parts by weight - light granulates (polystyrene balls) 10 parts by weight - liquid protein additive (hydrolysate of beef blood having a total content of proteins, polypeptides and amino acids included between 15 and 20% weight/volume) 10 parts by weight - mixing water 80 parts by weight The cement is homogenized (30 minutes), the mixing water containing the protein additive (30 seconds), the sand and the granulates are added, then mixed for 60 to 120 seconds in a mixer operating from 15 100 to 60 rum.
The concrete thus obtained may then be compacted, vibrated, then immediately removed from the mound to obtain prefabricated articles, or directly positioned after pumping, cold extrusion or projection on site .
After conservation in a damp atmosphere (100% RHO at 20C
for 7 days, this concrete presents an apparent density (MA) of 400 kg/m3, and (according to the measurements made on test pieces measuring 28 cm x 7 cm x 7 cm) a tensile-bending strength (TO) of 7 x 105 at 106 Pascal and a compressive strength (ARC) of 1.4 x 106 at 2.5 x 106 25 Pascal.
Eye comparison, the concrete obtained by replacing the 10 parts by weight of protein additive by 10 parts by weight of water, gives, under the same conditions:
MA: 350 kg/m3 To: 5 x 104 at 2 x 105 Pascal US 2 x 105 at 4 x 105 Pascal.
Concrete incorporating heavy granulates A concrete is obtained by proceeding as indicated in Example 1, from the following ingredients:
- hydraulic cement 260 parts by weight - gravel (having particles with a diameter of between 3 and 8 mm) 1400 parts by weight - sand 50 parts by weight - liquid protein additive (hydrolysate of beef blood having a total content of proteins, polypeptides and amino acids of 15 to 20% weight/volume) 10 parts by weight 10 - water 80 parts by weight This concrete, after conservation in a humid atmosphere (100%
RHO at 20C for 7 days, as indicated in Example 1, presents the following properties:
MA: 1800 kg/m3 TO: 2.3 x 106 Pascal ARC: go x 106 Pascal On the other hand, the product obtained by replacing the 10 parts by weight of protein additive by 10 parts by weight of water pro-sets, under the same conditions, the following properties:
MA: 1800 kg/m3 TO: 1.6 x 106 Pascal ARC: 7.8 x 106 Pascal.
The tests carried out with the construction materials obtained according to the invention with the protein additive coming from blood 25 or another source of protein show that said additive possesses a thickening power, a golfing power and an emulsifying power.
As far as the thickening power is concerned, it is observed that the protein additive according to the invention is capable of binding a certain quantity of water with a force which is the greater as it is 30 in intimate association therewith. This capacity to retain water brings about an expansion of the molecules of the protein additive, at the origin of an increase in the viscosity.
As far as the golfing power is concerned, it is observed that the protein additive, under the effect of setting of the hydraulic cements, 35 forms a three-dimensional matrix containing in its meshes the components of the construction material.
it Concerning the emulsifying power, a lowering of the interracial tension which exists between two non-miscible faces such as fat and water, is observed. The macromolecules and the protein additive presenting a lipophilic pole and a hydrophilic pole are placed essentially at the 5 interfaces of the drops. The hydrophilic pole in the water and the lip-Philip pole in the fat group together to form air bubbles. This results in a rearrangement which reduces or eliminates the interracial tension.
The construction materials according to the invention are useful in particular in the manufacture of numerous articles of construction.
10 The light concrete of Example I is particularly advantageous in the menu-lecture of bridge floors, it makes it possible to decrease the weight of the metallic structure, to ensure a better distribution of the overloads and, due to its insulating properties, to limit conduction of vibrations.
In the domain of highways and motorways, the concrete of 15 Example I makes it possible simultaneously (i) to ensure good protection with respect to the frost/thaw cycles, and (ii) to reduce the depth of the foundations. According to conventional techniques, a highway with dense traffic comprises, from top to bottom:
- - a layer of surfacing of 5 cm, - a bituminous layer of 18.5 cm, - a supporting layer of rolled granulates of 15 cm, an aerated layer for protection against frost of 45 cm, and - a so-called foundation layer of 20 am.
With the concrete of Example 1, the total thickness has Advent-25 juicily been reduced by replacing the supporting layer of rolled granulates and the frost-protection layer by one single layer of concrete of 22 cm, whilst giving the same protection with respect to the frost/thaw cycles.
The concretes according to the invention are also useful in 30 the preparation of hollow gauged bricks, noggins, roof slabs, prefabricated partitions and smoke flues.
By way of information, a mode of preparing the hydrolysate (stabilized protein) which may be used according to the invention will be described hereinafter:
100 liters of beef blood (collected from healthy animals) have 600 g of sodium citrate (anti-coagulant) added thereto within the 5 mix nuts following bleeding. This blood is then treated (within the 3 hours following bleeding) with lactic acid-producing bacteria (mixture of Streptococcus lactic, Leuconostoc mesenteroides and Lactobacillus easel) so that the bacterial population in the resulting medium is at least 105 5 germs/cm3, and 10 kg of carbohydrate (water-soluble starch), for 24 hours at 28C, the pi of the resultant medium always being less than 6 (as lactic acid is formed, the pi stabilizes at about 4.7).
Analysis of this hydrolysate conserved for 15 months, at a tempo-nature of between 15 and 20C and at a pi of about 4.7, gives the folio-10 wing results shown in Table I hereinafter with a total content of aminatednitrogen of 2.58%.
I
TABLE I
Components Composition in g/per 100 g - of protein hydrolysate Aspartic acid 2.22 Threonine 1.08 Shrine 1.13 Glutamic acid 2.01 Praline 0.839 Gleason 0.978 Ala nine 1.67 Valise 1.78 Sistine 0.313 Methionine 0.309 Isoleucine 0.196 Lawson 2.30 Tarzan 0.635 Phenylalanine 1.36 Lawson 1.91 Histidine 1.20 Asinine 0.767 Tryptophane 0.279 NH3 after hydrolysis (6 N HI 0.114
The invention recommends a novel technical solution for impure-vying the mechanical strengths (particularly the tensile, bending and come pressive strengths), for reducing sweating and segregation, and finally for improving the workability of the hydraulic cements, concretes and 35 mortars. This novel technical solution which favorably modifies a certain number of theological parameters, employs liquid protein hydrolysates which differ from the additives heretofore known in the building domain.
I I
The protein additive recommended according to the invention for improving the mechanical properties, the workability and for reducing sweating and segregation of the hydraulic cements, concretes and mortars?
is characterized in that it is a protein hydrolysate having a pi less .
than or equal to 6, comprising substances selected from -the group keenest-tuned by proteins, polypeptides, amino acids and mixtures thereof, and obtained by treating 100 parts by weight of an aqueous composition contain nine at least one protein substance selected from the group constituted 5 by proteins, polypeptides and mixtures thereof, with at least one bacterial strain producing lactic acid having a population greater than or equal to 102 germs/cm3, in the presence of 0.5 to 30 parts by weight of a source of carbon belonging to the family of carbohydrates, for at least 2 hours, at a temperature of between 0 and 65C and at a pi less than 10 or equal to 6.
The protein hydrolysate useful according to the invention in the construction domain may be used directly in the liquid or humid state. Before being associated with a hydraulic cement and with water, or as the case may be, with a hydraulic cement, water with sand and/or 15 granulates, it may be conserved in a suitable recipient for at least 18 months at a temperature of between -5 and +60C.
The protein additive according to the invention differs, by the mode by which it is obtained, from the means recommended by German Patent No. 511 513 on the one hand and the summary of Chemical Abe 20 streets 88, 140 835 t, on the other hand.
Among suitable protein hydrolysates, particular mention may be made of those obtained from animal or plant proteins. Among these proteins, mention may be made of proteins of animal origin such as meat product proteins, offal product proteins, milk proteins, whole fish 25 proteins, fish wastes, albumins (particularly egg albumin), and plant proteins such as those contained in the Leguminous, oleaginous plants, Sullenness (particularly tobacco) and algae.
Protein substances which are suitable for obtaining the hydra-Lucite according to the invention are in particular the animal and plant 30 proteins mentioned above as well as the hydrolysates and proteolysates of said animal and plant proteins which comprise, in particular, either proteins which have not yet broken down, or polypeptides, or mixtures of proteins and polypeptides, in association, as the case may be, with amino acids.
The ground meat product proteins or the ground or liquid offal ~2~g~
product proteins are advantageously rapidly subjected to treatment with bacteria producing lactic acid. Before such treatment, especially if it is delayed, it is recommended to associate with the protein substances I to 15% by weight of crushed cereals.
The following bacteria producing lactic acid may be used in the preparation of the hydrolysate useful according to the invention as additive in the construction domain: Streptococcus (particularly Streptococcus bevies Streptococcus thermophilus, Streptococcus focalize S ptococcus faecium, Streptococcus creamers, Streptococcus lactic), 10 Leuconostoc (particularly Leuconostoc mesenteroides, Leuconostoc lactic, Leuconostoc creamers) and Lactobacillus (particularly Lactobacillus delbrueckii, Lactobacillus leichmanii, Lactobacillus jensenii, Lactobacillus lactic, Lactobacillus bul~aricus, Lactobacillus helveticus, Lactobacillus acidophilus, Lactobacillus easel, Lactobacillus planetarium). Among suitable 15 strains, particular mention may be made of the strains of the Collection of -the Pasteur Institute: Streptococcus bevies 56.23~ Streptococcus _hermophilus 66.31~ Streptococcus focalize 54.32~ Streptococcus faecium 54.31~ Streptococcus lactic 70.57, Leuconos-toc mesenteroides aye Lactobacillus delbrueckii 57.8~ Lactobacillus leichmanii 53.61~ 53.3 and 20 53.4, Lactobacillus jensenii 69.17~ Lactobacillus bul~aricus 71.36~ Lookout-bacillus helveticus 57.15~ Lactobacillus acidophilus 76.13 and 71.34 Lactobacillus easel 71.37~ 71.38 and A 158~ Lactobacillus planetarium 71.39~
and the strain of the catalog of the American Type Culture Collection:
Lactobacillus lo ATTICS 8000.
According to the invention, one or more strains of lactic acid-producing bacteria will be used. The bacterial population will be between 102 germs/cm3 and 108 germs/cm3, and advantageously between 103 germs/
cm3 and 106 germs/cm3.
The total content of protein substance and amino acid contained 30 in the liquid protein hydrolysate according to the invention is between 0.5 and 50% weight/volume. If necessary, the protein hydrolysate may be concentrated in vacua and/or sterilized.
The carbohydrates used as source of carbon may be hydrolyzable or non-hydrolyzable, the preferred carbohydrates being in particular 35 glucose, lactose! succors, maltose, water-soluble starch and whey.
~lZ2~6~
It is possible to select the or each bacterial strain which may be used according to the invention by referring on the one hand to the intrinsic stability of the liquid protein hydrolysate obtained and on the other hand to a test of use which may be described as follows:
Two concretes A and B, of the following composition, are made:
A B
- cement of CP5 45 type with fillers 400 g 400 g - lime, type HA 40 g 40 g 10 - light granulate 2 1 2 1 (polystyrene, I to 5 mm diameter) - additive 0 22 g The role of the additive according to the invention added to concrete B will be a densification of said concrete equivalent to at least 10 per cent of entrained air.
According to the invention, a process for manufacturing a con-struction element from a hydraulic cement, water and a liquid protein additive is recommended, wherein 100 parts by weight of hydraulic cement are mixed with 0.001 to 10 parts by weight of liquid protein additive 20 previously diluted with mixing water. 20 to 50 parts by weight of mixing water for 100 parts by weight of hydraulic cement will advantageously be used.
According to this process, sand and/or granulates, which may be light and possibly expanded (polystyrene balls, glass balls, mica, vermin quilt) or heavy depending on the desired density of the construction material, may also be introduced.
Four types of material may be obtained by the process of the invention, namely:
material A, from 30 - 100 parts by weight of hydraulic cement, and - 0.001 to 10 parts by weight of protein additive;
material B, from - 100 parts by weight of hydraulic cement, ~2g~
- 0.001 to 10 parts by weight of protein additive, and - I to 9000 parts by weight of sand;
material C, from - 100 parts by weight of hydraulic cement, - 0.001 to 10 parts by weight of protein additive, and - I to 90000 parts by weight of granulates; and material D, from - 100 parts by weight of hydraulic cement, - 0.001 to 10 parts by weight of protein additive, - I to 9000 parts by weight of sand, and - I to 90000 parts by weight of granulates.
The best embodiment of the invention consists, to obtain a construction material, in mixing 100 parts by weight of hydraulic cement (particularly cement or blast furnace slag) with 0.001 to 10 parts by weight of protein additive previously diluted in, preferably, 30 to 35 parts by weight of water with, as the case may be, sand and/or light or heavy granulates, the protein additive being obtained from liquid animal blood which is one of the elements of offal. The fresh animal blood which is collected at the abutter must have an anti-coagulant added thereto (particularly an anti-coagulant selected from the group constituted by the alkali metal citrates, polyphosphates, heparin and silicones) within the five minutes following bleeding. 0.05 to I part by dry weight of anti-coagulant will advantageously be incorporated with 100 parts by weight of fresh liquid blood, treatment with the bacteria producing lactic acid being carried out at the latest 6 hours after bleeding.
It is unnecessary to employ a particular mixer as indicated in US. Patent No. 4 203 674 mentioned above, the cement is mixed with mixing water containing the protein additive, then, as the case may be, sand and/or granulates, in a conventional mixer operating at 30 50-100 rum.
Other advantages and features of the invention will be more readily understood on reading the following description of embodiments which are in no way limiting but given by way of illustration.
EXAMPLE I
Concrete incorporating hi granulates 6~2~
A concrete is prepared from the following ingredients:
- hydraulic cement 250 parts by weight - sand having particles with a diameter smaller than or equal to 0.8 mm 50 parts by weight - light granulates (polystyrene balls) 10 parts by weight - liquid protein additive (hydrolysate of beef blood having a total content of proteins, polypeptides and amino acids included between 15 and 20% weight/volume) 10 parts by weight - mixing water 80 parts by weight The cement is homogenized (30 minutes), the mixing water containing the protein additive (30 seconds), the sand and the granulates are added, then mixed for 60 to 120 seconds in a mixer operating from 15 100 to 60 rum.
The concrete thus obtained may then be compacted, vibrated, then immediately removed from the mound to obtain prefabricated articles, or directly positioned after pumping, cold extrusion or projection on site .
After conservation in a damp atmosphere (100% RHO at 20C
for 7 days, this concrete presents an apparent density (MA) of 400 kg/m3, and (according to the measurements made on test pieces measuring 28 cm x 7 cm x 7 cm) a tensile-bending strength (TO) of 7 x 105 at 106 Pascal and a compressive strength (ARC) of 1.4 x 106 at 2.5 x 106 25 Pascal.
Eye comparison, the concrete obtained by replacing the 10 parts by weight of protein additive by 10 parts by weight of water, gives, under the same conditions:
MA: 350 kg/m3 To: 5 x 104 at 2 x 105 Pascal US 2 x 105 at 4 x 105 Pascal.
Concrete incorporating heavy granulates A concrete is obtained by proceeding as indicated in Example 1, from the following ingredients:
- hydraulic cement 260 parts by weight - gravel (having particles with a diameter of between 3 and 8 mm) 1400 parts by weight - sand 50 parts by weight - liquid protein additive (hydrolysate of beef blood having a total content of proteins, polypeptides and amino acids of 15 to 20% weight/volume) 10 parts by weight 10 - water 80 parts by weight This concrete, after conservation in a humid atmosphere (100%
RHO at 20C for 7 days, as indicated in Example 1, presents the following properties:
MA: 1800 kg/m3 TO: 2.3 x 106 Pascal ARC: go x 106 Pascal On the other hand, the product obtained by replacing the 10 parts by weight of protein additive by 10 parts by weight of water pro-sets, under the same conditions, the following properties:
MA: 1800 kg/m3 TO: 1.6 x 106 Pascal ARC: 7.8 x 106 Pascal.
The tests carried out with the construction materials obtained according to the invention with the protein additive coming from blood 25 or another source of protein show that said additive possesses a thickening power, a golfing power and an emulsifying power.
As far as the thickening power is concerned, it is observed that the protein additive according to the invention is capable of binding a certain quantity of water with a force which is the greater as it is 30 in intimate association therewith. This capacity to retain water brings about an expansion of the molecules of the protein additive, at the origin of an increase in the viscosity.
As far as the golfing power is concerned, it is observed that the protein additive, under the effect of setting of the hydraulic cements, 35 forms a three-dimensional matrix containing in its meshes the components of the construction material.
it Concerning the emulsifying power, a lowering of the interracial tension which exists between two non-miscible faces such as fat and water, is observed. The macromolecules and the protein additive presenting a lipophilic pole and a hydrophilic pole are placed essentially at the 5 interfaces of the drops. The hydrophilic pole in the water and the lip-Philip pole in the fat group together to form air bubbles. This results in a rearrangement which reduces or eliminates the interracial tension.
The construction materials according to the invention are useful in particular in the manufacture of numerous articles of construction.
10 The light concrete of Example I is particularly advantageous in the menu-lecture of bridge floors, it makes it possible to decrease the weight of the metallic structure, to ensure a better distribution of the overloads and, due to its insulating properties, to limit conduction of vibrations.
In the domain of highways and motorways, the concrete of 15 Example I makes it possible simultaneously (i) to ensure good protection with respect to the frost/thaw cycles, and (ii) to reduce the depth of the foundations. According to conventional techniques, a highway with dense traffic comprises, from top to bottom:
- - a layer of surfacing of 5 cm, - a bituminous layer of 18.5 cm, - a supporting layer of rolled granulates of 15 cm, an aerated layer for protection against frost of 45 cm, and - a so-called foundation layer of 20 am.
With the concrete of Example 1, the total thickness has Advent-25 juicily been reduced by replacing the supporting layer of rolled granulates and the frost-protection layer by one single layer of concrete of 22 cm, whilst giving the same protection with respect to the frost/thaw cycles.
The concretes according to the invention are also useful in 30 the preparation of hollow gauged bricks, noggins, roof slabs, prefabricated partitions and smoke flues.
By way of information, a mode of preparing the hydrolysate (stabilized protein) which may be used according to the invention will be described hereinafter:
100 liters of beef blood (collected from healthy animals) have 600 g of sodium citrate (anti-coagulant) added thereto within the 5 mix nuts following bleeding. This blood is then treated (within the 3 hours following bleeding) with lactic acid-producing bacteria (mixture of Streptococcus lactic, Leuconostoc mesenteroides and Lactobacillus easel) so that the bacterial population in the resulting medium is at least 105 5 germs/cm3, and 10 kg of carbohydrate (water-soluble starch), for 24 hours at 28C, the pi of the resultant medium always being less than 6 (as lactic acid is formed, the pi stabilizes at about 4.7).
Analysis of this hydrolysate conserved for 15 months, at a tempo-nature of between 15 and 20C and at a pi of about 4.7, gives the folio-10 wing results shown in Table I hereinafter with a total content of aminatednitrogen of 2.58%.
I
TABLE I
Components Composition in g/per 100 g - of protein hydrolysate Aspartic acid 2.22 Threonine 1.08 Shrine 1.13 Glutamic acid 2.01 Praline 0.839 Gleason 0.978 Ala nine 1.67 Valise 1.78 Sistine 0.313 Methionine 0.309 Isoleucine 0.196 Lawson 2.30 Tarzan 0.635 Phenylalanine 1.36 Lawson 1.91 Histidine 1.20 Asinine 0.767 Tryptophane 0.279 NH3 after hydrolysis (6 N HI 0.114
Claims (10)
1. A protein additive for hydraulic cements, mortars and concretes, useful for improving the mechanical properties and the workability and for reducing sweating and segregation, wherein it is a protein hydrolysate having a pH less than or equal to 6, comprising substances selected from the group constituted by proteins, polypeptides, aminoacids and mixtures thereof, and obtained by treating 100 volumes of an aqueous composition containing at least one protein substance selected from the group constituted by proteins, polypeptides and mixtures thereof, with at least one bacterial strain producing lactic acid having a population greater than or equal to 102 germs/cm3, in the presence of 0.5 to 30 parts by weight of a source of carbon belonging to the family of carbohydrates, for at least 2 hours, at a temperature of between 0 and 65°C and at a pH less than or equal to 6.
2. The additive of Claim 1, wherein the protein substance used as raw material subjected to the treatment with at least one strain of lactic acid-producing bacteria is selected from meat product proteins, offal product proteins, milk proteins, whole fish proteins, fish waste proteins, albumins, proteins of Leguminosae, oleaginous plants, Solanaceae and of algae.
3. A protein additive for hydraulic cements, mortars and concretes, useful for improving the mechanical properties and the workability and for reducing sweating and segregation, wherein it is a protein hydrolysate having a pH less than or equal to 6, comprising substances selected from the group constituted by proteins, polypeptides, aminoacids and mixtures thereof, and obtained by treating 100 volumes of an aqueous composition containing at least one protein substance selected from the group consti-tuted by liquid animal blood to which an anticoagulant is added, the other offal proteins, meat product proteins, whole fish proteins, fish waste proteins and mixtures thereof, with at least one bacterial strain producing lactic acid having a population greater than or equal to 102 germs/cm3, in the presence of 0.5 to 30 parts by weight of a source of carbon belonging to the family of carbohydrates, for at least 2 hours, at a temperature of between 0 and 65°C and at a pH less than or equal to 6.
4. A protein additive for hydraulic cements, mortars and concretes, useful for improving the mechanical properties and the workability and for reducing sweating and segregation, wherein it is a protein hydrolysate having a pH less than or equal to 6, comprising substances selected from the group constituted by proteins, polypeptides, aminoacids and mixtures thereof, and obtained by treating 100 volumes of an aqueous composition containing at least one protein substance constituted by liquid animal blood to which an anticoagulant is added, with at least one bacterial strain producing lactic acid having a population greater than or equal to 102 germs/cm3, in the presence of 0.5 to 30 parts by weight of a source of carbon belonging to the family of carbohydrates, for at least 2 hours, at a temperature of between 0 and 65°C and at a pH less than or equal to 6.
5. The additive of Claim 4, wherein the protein substance contains 0.05 to 1 part by dry weight of anticoagulant for 100 parts by weight of liquid animal blood.
6. A process for manufacturing a construction element from a hydraulic cement and a protein additive according to Claim 1, comprising the step of mixing 100 parts by weight of hydraulic cement with 0.001 to 10 parts by weight of protein additive.
7. The process of Claim 6, wherein 20 to 50 parts by weight of mixing water for 100 parts by weight of hydraulic cement are used.
8. The process of either one of Claims 6 and 7, wherein:
- 100 parts by weight of hydraulic cement, - 0.001 to 10 parts by weight of protein additive, and - 1 to 9000 parts by weight of sand are used.
- 100 parts by weight of hydraulic cement, - 0.001 to 10 parts by weight of protein additive, and - 1 to 9000 parts by weight of sand are used.
9. The process of either one of Claims 6 and 7, wherein:
- 100 parts by weight of hydraulic cement, - 0.001 to 10 parts by weight of protein additive, and - 1 to 90000 parts by weight of granulates are used.
- 100 parts by weight of hydraulic cement, - 0.001 to 10 parts by weight of protein additive, and - 1 to 90000 parts by weight of granulates are used.
10. The process of either one of Claims 6 and 7, wherein:
- 100 parts by weight of hydraulic cement, - 0.001 to 10 parts by weight of protein additive, - 1 to 9000 parts by weight of sand, and - 1 to 90000 parts by weight of granulates are used.
- 100 parts by weight of hydraulic cement, - 0.001 to 10 parts by weight of protein additive, - 1 to 9000 parts by weight of sand, and - 1 to 90000 parts by weight of granulates are used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000462998A CA1229629A (en) | 1984-09-12 | 1984-09-12 | Additive of protein nature for hydraulic cements, mortars and concretes, and use thereof in the field of construction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000462998A CA1229629A (en) | 1984-09-12 | 1984-09-12 | Additive of protein nature for hydraulic cements, mortars and concretes, and use thereof in the field of construction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1229629A true CA1229629A (en) | 1987-11-24 |
Family
ID=4128701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000462998A Expired CA1229629A (en) | 1984-09-12 | 1984-09-12 | Additive of protein nature for hydraulic cements, mortars and concretes, and use thereof in the field of construction |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1229629A (en) |
-
1984
- 1984-09-12 CA CA000462998A patent/CA1229629A/en not_active Expired
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