Method for the protection of concrete in sea water
FIELD OF THE INVENTION 
     My present invention relates to methods for the protection of concrete in sea water and other biologically active waters. 
     BACKGROUND OF THE INVENTION 
     Methods and biocides are known for combating the biodegradation of waters by fouling agents. Romanian Pat. No. 57,257, representative of this prior art, discloses a solution containing biocidal substance only, within a suitable solvent, and having a viscosity adapted to promote deep capillary pentration into the concrete. 
     The disadvantages of the prior art as exemplified by that patent are: 
     (a) the necessity to apply four layers of paint; 
     (b) no provision for strengthening the surface structure of the cured concrete; 
     (c) does not change the biocide used in accordance with the particular fouling agents present; 
     (d) makes no provision for a supplementary mechanical-fixation treatment with biocide at the same time--apart from the basic treatment with biocide itself--such provision being necessary where the friction phenomenon is significant; 
     (e) makes no provision for the separate application of both biocides in stages. 
     OBJECT OF THE INVENTION 
     The object of my present invention, therefore, is to provide a method of treating concrete surfaces immersed in sea water and other biologically active waters, to prevent fouling of such concrete surfaces while avoiding the drawbacks of conventional methods including those enumerated above. 
     SUMMARY OF THE INVENTION 
     I realize this object, in accordance with my invention, by the provision of a method which comprises three separate stages of treatment, namely: 
     (a) fluating of concrete surfaces resulting in their simultaneous strengthening and anti-fouling protection by means of an aqueous solution having 3-5% by weight fluorosilicic acid or calcium, magnesium or zinc fluorosilicate applied by painting or spryaing; 
     (b) treatment against biodeterioration by means of a complex solution of 45-50% biocide by weight within a common organic solvent, for instance white-spirit, the application being effected by painting or spraying in one or two coats; and 
     (c) fixation treatment by a fungicide solution of synthetic resins, e.g. polyesters or epoxides, in a proportion of 4-6% by weight within the solution used in the second stage (b). The application is carried out as mentioned above. 
     The solutions employed in the above three stages all possess a viscosity enabling a deep capillary penetration into the porous medium of the concrete to be protected. 
     The biocide compounds which can be used either separately or together in practicing the method of my invention are: copper naphthenate, betanaphthol, pentrachlorophenol, tributyltin oxide and fluorosilicic acid. 
     In accordance with a feature of the invention, the composition of a solution containing any of the above biocides is varied in strength according to the fouling agents encountered in the waters surrounding the concrete to be protected, such selected strengths being based on the toxicity spectrum of the biocide. Where several biocides are used together, i.e. mixed in solution, I prefer to add them in equal parts. All dosages are by weight. 
     Pursuant to a further feature of my invention, the fixation treatment is carried out by applying to the concrete surfaces a fungicide solution of synthetic resins, e.g. polyesters or epoxides, as described in more detail hereinafter. 
    
    
     SPECIFIC DESCRIPTION AND EXAMPLES 
     The method of my invention for protecting concrete immersed in sea water and other biologically active waters consists in the application--during three successive stages of which one or two may be omitted or inverted under certain conditions--of treatments in accordance with the following examples. 
     EXAMPLE 1 
     Fluating 
     Fluating is done by means of a solution in water of 3-5% fluorosilicic acid, Ca, Zn or Mg fluorosilicate (dosage by weight), the rate of the active substance being increased by one percent according to the saltiness of the sea water, i.e. for intervals up to 15%O, between 15-25%O and over 25%O. 
     EXAMPLE 2 
     Treatment Against Biodeterioration of Concrete Surfaces 
     This treatment is carried out by the use of biocide compounds or substances, as prescribed hereinafter, according to the nature of the concrete-surface fouling agents and the number of germs contained in a volume unit of the biologically active water. 
     Treatment applications are provided in one to two coatings depending on the number of germs (bacteria sulphate reducing agent) present in the unit of volume of biologically active water, thus: 
     1 coat if between 10 5  and 5×10 5   
     2 coats if between 5×10 6  and 10 6   
     Any of the following biocide compounds may be used in the above treatment: 
     copper naphthenate, active against the majority of fouling agents; there is utilized a 94% copper naphthenate solution diluted with 50% white-spirit (by weight) in a proportion of 5-10 parts copper naphthenate solution to 9.0-9.5 parts white-spirit (by weight); 
     betanaphthol, active against filamentous or fibrous sea algae and winding worms; there is utilized a 12% betanaphthol solution in white-spirit (by weight) further diluted in a proportion of 5-10 parts solution to 9.0-9.5 parts white-spirit (by weight); 
     pentachlorophenol, active against the majority of fouling agents; there is utilized a solution of 12% pentachlorophenol in white-spirit (by weight), further diluted in the same proportions as given for betanaphthol; 
     tributyl tin oxide, active against the majority of fouling agents. Utilize a 6% tributyl tin oxide solution in white-spirit (by weight), further diluted in a proportion of 5-10 parts solution to 9.0-9.5 parts white-spirit (by weight). 
     When several compounds are used, depending on the toxicity spectrum specific to each of them, their mixing is in equal parts. 
     EXAMPLE 3 
     Fixation Treatment 
     The fixation treatment is performed by means of a biocide solution according to the compositions set forth under Example 2, to which a 4-6% polyester or epoxy resin solution in volume is added having the following compositions (the rate and parts being indicated by weight): 
     polyesteric resin solution accelerated by 0.5-0.8% cobalt octoate (6% cobalt in octoate) 12 parts, monostyrene as solvent 10 parts; to the utilized quantity of resin peroxide of methyl-ethyl-ketone 50% solution in dibutylphthalate 0.25 parts are added to start the polymerization. 
     epoxy resin solution with 5-45% hardener according to the type of resin (see below); to the 10 parts of solvent (8 parts toluene and 2 parts ethylic or methylic alcohol) 12 resin parts with hardener are added. 
     There are listed below several compositions of epoxydic resin solution type ARALDITE, made by CIBA-GEIGY, Switzerland, in which the quantity of resin represents 3% of the weight of the indicated solvent. 
     
         ______________________________________                                    
Resin         Hardener     Admixture                                      
______________________________________                                    
AY 101        HY 951       --                                             
100 parts     5-6 parts                                                   
AY 101        HY 956       --                                             
100 parts     10-12 parts                                                 
AY 121        HY 951       --                                             
100 parts     4-4,5 parts                                                 
CY 221        HY 837       Silane A 186                                   
100 parts     25 parts     1 part                                         
GY 250        X 157 2273   --                                             
100 parts     15 parts                                                    
DY 022        HY 2954      --                                             
100 parts     45 parts                                                    
LY 554        HY 554       --                                             
100 parts     20 parts                                                    
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     The technique of application of the treatments in Examples 1, 2 and 3 is as follows: 
     The fluating (Example 1) is performed applying 1-2 coats with 30 minutes intermission by painting or spraying with a compressed air gun (5-6 atm.). The biocide treatment that follows, as per Example 2, is applied 24 hours after fluating. 
     The biocide treatment (Example 2) is applied in 1-2 coats, the second one 30 minutes after the first coat. The fixation treatment, as per Example 3, may be carried out 1 hour after the biocide treatment. 
     The fixation treatment (Example 3) is applied in 1-2 coats, the interval of time between the two coats being at least 1 hour. 
     The foregoing three stages of treatment need not all be applied but, depending on the degree of hostility of the environment, may be applied only singly, i.e. any of the stages alone, or in combinations of two or three of them. The application of stages 1 and 2 may be made in reverse order as may at times be deemed appropriate. 
     The advantages of the method, solutions and technology of the present invention, as described above, for the protection of concrete immersed in sea water and other biologically active waters, are: 
     penetrability to depths of about 10 mm into the thickness of the concrete, utilizing its porous structure for a good fixation in depth; 
     the application is easily done by a mere surface treatment; 
     the application entails easy access and cheap materials; 
     besides the bioprotection a cured surface is obtained; 
     the treated surface has a large toxicity spectrum and an unlimited life; 
     permits the resumption of concreting without sanding; 
     enables the immersion in sea water of the concrete, reinforced concrete or prestressed concrete prefabs before the maturation of the cement stone (hard cement), i.e. immersion in only 1-2 weeks instead of 1-2 months; enables, thanks to the fixation treatment, the utilization in sea water of supply lines heretofore subjected to the detrimental effects of fixation fouling in sewer systems and at sites of marine construction of reinforced or prestressed concrete slips; 
     permits reducing the concrete covering layer of reinforcements at reinforcing or prestressing concrete works both in sea water and sea environment, i.e.: 
     in sea water, in estuaries or river deltas (salinity under 15%O) and up to 2 m above the water level, the concrete covering is reduced from 5 cm to 4 cm when the concrete used has a permeability of 4 and a water/cement factor of 0.6; 
     in normal sea water (salinity between 15%O and 35%O) the concrete covering is reduced from 6 cm to 4.5 cm independent of the diameter of reinforcement if there are applied the three protection stages on a concrete with a permeability of 8 and a water/cement factor of 0.5; 
     in sea environment, independent of the saltiness thereof, the concrete covering is reduced from 3 cm to 2 cm if the three protection stages are applied and to 2.5 cm if only stages 1 and 3 are applied.