COATING MATERIAL FOR TENDON FOR PRESTRESSED CONCRETE, AND METHOD OF MAKING PRESTRESSED CONCRETE ARTICLES

Abstract: A coating material for a tendon for prestressed concrete including a curing composition the curing time of which is so controlled that the composition is held in an uncured fluid state for a predetermined time after the concrete hardens. After the predetermined time passes, the composition cures to protect the tendon against corrosion and adhere it to the concrete. The invention includes also a method of making prestressed concrete using such a coating material.

Description: The present invention relates to coatings material for tendon for prestressed concrete, which is to be coated on the surface of tendons used in post-tensioning prestressed concrete systems in order to keep tendons from rust and corrosion and integrate them with the concrete. Post-tensioning which is a typical method for manufacturing prestressed concrete, is usually carried out as follows. A tendon, such as prestressing steel (steel wire, steel strand, steel bar or the like) is inserted in a metal sheath. Concrete is then poured around it. After the concrete hardens, tension is applied to the tendon. Then, cement milk or the like grouting medium is injected between the sheath and the tendon for the purpose of preserving the tendon from rust and corrosion and integrating the tendon with the concrete. However, the operations of inserting the tendon in a sheath and injecting cement milk are troublesome and take much time and labour, which raises the cost of manufacture. Further, the gap between tendon and sheath is very narrow and generally a tendon is curved or twisted in the concrete, so that the medium can not be properly injected through the whole length of the tendon. Accordingly, there is a likelihood that the tendon corrodes at portions where there was insufficient injection. In order to solve the abovementioned problems it has been proposed to pre-coat a coating material on the surface of a tendon. These methods can be substantially divided into the following two groups: (1) for obtaining antirust and anticorrosion effects, (2) for preventing the tendon from attaching to the concrete. An example of the first type of method is one which electrostatically coats the surface of a tendon of prestressing steel with an epoxy-resin as coating material. This method can obtain antirust and anticorrosion effects. However, because the coating material comes into a completely cured state after coating, the tendon must be inserted in a sheath and grout to integrate the tendon with the concrete, as in the conventional post-tensioning system. Another method, which falls in both the abovementioned groups (1), (2), uses so-called unbonded prestressing steel, which is coated with grease and then covered with polyethylene or the like. This method in which the treated prestressing steel is positioned before pouring concrete and tension is applied to the unbounded prestressing steel after the concrete hardens, has the advantage that the tension applied to the prestressing steel can be transmitted to the whole length of the prestressing steel because of the presence of the fluid grease between the prestressing steel and the concrete. As a result, the metal sheath used in the conventional post-tensioning system is not required, which naturally eliminates insertion of a tendon in a sheath, injection of cement milk and grouting. Accordingly, the disadvantage which causes the expense of the conventional post-tensioning system can be eliminated. However, since the grease coating material does not harden, this is at the cost of the tendon not adhering to the concrete forever, which consequently reduces the bending strength and the fatigue strength of the concrete. In order to eliminate the abovementioned disadvantage of the unbonded prestressing steel method, a method has been proposed which comprises coating a prestressing steel with a thermosetting composition in uncured state, positioning the steel as before, and after applying tension to the prestressing steel, curing the coated thermosetting composition by heating the steel by means of high-frequency heating or the like so as to make the steel adhere to the concrete. However, this method which needs heating of the tensioned prestressing steel is very dangerous. Further, it is impossible to accurately heat only a predetermined steel in a large-sized concrete construction and overall adhesion in any given structure cannot be assured. AT-201280 alleges the use of an epoxy coating material for coating tendons. In order to solve the above mentioned problems, an object of the present invention is to provide coating material for tendons for prestressed concrete which permits forming prestressed concrete articles at a reduced cost, while assuring the antirust and anticorrosion effects of the tendon and adherence of the tendon to the concrete. According to the present invention, the use of a coating material for coating a tendon for incorporation into prestressed concrete is disclosed, the coating material comprising a curing composition, the curing time of which is controlled so as to cure in a predetermined atmosphere in a predetermined time after the concrete hardens is provided; it includes 100 parts of epoxy resin, a latent curing agent and 0.03 to 0.5 parts by weight of a curing accelerator is provided, the latent curing agent being one of dihydrazide, diphenyldiaminosulphone, dicyandiamide, 2-methylimidazole and derivative thereof or BF₃ amine complex, the curing accelerator being a tertiary amine, the coating material taking at least three days to cure at ambient temperature. The invention also includes the use of such a material for coating a tendon for prestressed concrete. In use, the tendon is coated with coating material for tendon for prestressed concrete according to the present invention and arranging the tendon in the concrete, the coating material on the surface of the tendon is kept in an uncured and fluid state for a predetermined time after the concrete hardens. After the predetermined time, the coating material surely comes into a cured state. Consequently, by applying tension to the tendon when the coating material on the surface of the tendon is still in the uncured state, the tension can be transmitted to the tendon over the whole length thereof and the tendon can be made to surely adhere to the concrete after the coating material is cured. Further, since the tendon is coated with the coating material, antirust and anticorrosion of the tendon can be surely obtained. As abovementioned, with the use of the coating material for tendon for prestressed concrete according to the present invention, prestressed concrete of good quality can be obtained only by coating a tendon with the coating material and arranging the tendon in the concrete. Consequently, the operations of inserting a tendon in a sheath and grouting, which are required in the conventional post-tensioning system, can be omitted. Accordingly, it is possible to lower the cost of manufacturing prestressed concrete. Fig. 1 is a sectional view showing a used state of an embodiment of coating material for tendon for prestressed concrete according to the present invention; Fig. 2 is a sectional view showing used state of the embodiment of Fig. 1 ; Fig. 3 is a graph showing relationship between the curing time and the shear adhesive strength of the embodiment of Fig. 1 ; Fig. 4 is a graph showing relationship between the lapse of time after placing concrete and the coefficient of friction; Fig. 5 is a graph showing relationship between the relative sliding amount of a tendon to the concrete and the pulling load; Fig. 6 is a graph showing relationship between the deflection amount at opposite end supports of a concrete beam and the bending load; and Fig. 7 is a graph showing relationship between the composition ratio of a curing accelerator in the embodiment of Fig. 1 and the number of days required for curing. A curing composition according to the present invention basically consists of a resin which is itself uncured at ordinary temperature and a latent curing agent which chemically cures the resin. However, a curing accelerator may be added to the composition, if necessary. Further, a filler, additives and the like may be added, too. The curing time of the curing composition can be controlled by changing the kinds and amounts of the latent curing agent and the curing accelerator. As an example, a coating material includes an epoxy-resin curing composition which has, as a principal constituent, an epoxy-resin which is uncured at ordinary temperature and which consists of an epoxy-resin, a diluent, a latent curing agent, a curing accelerator, a filler and additives. As the epoxy-resin, used are are liquid polyepoxides having more than two epoxy radicals per molecule and being polyglycizyl compounds of polyhydric phenols such as 2, 2 - bis (4- hydroxyphenyl) propane (popularly named bisphenol A), bis (4- hydroxyphenyl) methane (popularly called bisphenol F), 1, 1 - bis (4 - hydroxyphenyl) ethane (popularly called bisphenol AD) , 2, 2 - bis (3, 5 dibromo - 4 - hydroxyphenyl) propane (popularly called TBA), hydroquinone and resorcine. Further, polyglycidyl compounds of polyhydric alcohols such as ethylene glycohol and glycerine and polyhydric carboxylic acid such as phthalic acid can be also used as the epoxy-resin. As the diluent, a widely used reactive diluent such as n-butylglycizyl ether, an ester of phthalic acid such as dioctylphthalate, benzyl alcohol, fluphryl alcohol and other denatured aromatic polymer oils and the like can be used. As the latent curing agent, the following substances which are stable for a long time at normal temperature can be used; for example, dihydrazides such as dihydrazide adipate and dihydrazide sebacate, diphenyldiaminosulphone, dicyandiamide, 2-metylimidazol and their derivatives, BF₃ · amine complex and the like. As the curing accelerator, tertiary amines such as 2, 4, 6, - tris (N, N- dimethylaminomethyl) phenol, N, N-benzylmethylamine and the like can be used. The filler is added for the purpose of controlling viscosity, thixotropic property and the like, and calcium carbonate, talc, silica and the like can be used as the filler. The additive is added for the purpose of dispersing filler and preventing precipitation of filler, and commercial aerosil and the like can be used as the additive. The mixing ratio of the constituents of the coating material will be described. The mixing ratio of the epoxy-resin and the latent curing agent is changed with the kinds of the epoxy-resin and the latent curing agent. When a latent curing agent having an active hydrogen such as dihydrazide is used, the molar ratio of the latent curing agent to the epoxy radical of the epoxy-resin is preferably 1: 0.5 to 2.0. On the other hand, when an ionic curing agent such as BF₃ · amine complex, tertiary amine or the like is used, the ratio of the latent curing agent to the epoxy-resin is preferably 0.5 to 1.0 phr (a part per hundred parts of resin). The amount of the curing accelerator is preferably 0.05 to 0.5 phr and the amounts of the diluent and filler are preferably determined in consideration of the viscosity of the composition. When a coating material according to the present invention is used in the post tensioning system, after coating the coating material on the surface of a tendon, the tendon is arranged in a predetermined position and then concrete is placed. After the concrete attains a predetermined strength, tension is applied to the tendon. Fig. 1 shows a tendon coated with a coating material of the present invention which is placed in prestressed concrete. In Fig. 1, indicated at 1 is coating material, 2 is a prestressing steel wire or tendon, and 3 is prestressed concrete. As shown in Fig. 2, the coating material 1 may be covered with a sheath 4 having a spiral recess. The sheath may be made of metal such as usual steel, or resin such as polyethylene or the like. It takes 3 days to 2 weeks for concrete to attain a predetermined strength after placing. The coating material must not cure before the concrete attains the predetemined strength. For the reasons, the coating material is preferably controlled so as to cure in at least more than 3 days after making the coating material (i. e. mixing curing compositions). Further, it is preferable that the coating material cures so rapidly after applying tension as to assure integration of the concrete with the tendon. Accordingly, the coating material is preferably controlled so as to cure within one year. The thickness of coated layer of the coating material is preferably 20 µm or more. This is for reasons that if the thickness is less than 20 µm, pinholes are apt to take place in the layer, so that the anticorrosion effect lowers, and the tendon and the concrete are not sufficiently separated from each other when the tension is applied to the tendon, so that the coefficient of friction increases. The coating material may be coated by brushing, dipping or the like. The coating way is not limited. The present invention will be described in more detail by means of examples. Example 1 To 90 parts of epoxy-resin of bisphenol A type (epoxy equivalents; 189, viscosity; 130 poise), 10 parts of benzyl alcohol as a diluent, 7 parts of dicyandiamide as a latent curing agent, 0.12 part of 2, 4, 6-tris (N, N- dimethyaminomethyl) phenol as a curing accelerator, 50 parts of tarc as a filler and 1 part of aerosil as an additive were added and stirredly mixed. A coating material including a curing composition was then obtained. This coating material is called Sample 1. Relationship between the curing time and the shear adhesive strength (iron / iron) of the coating material of Sample 1 in an atomosphere having a temperature of 20 °C was examined. The result is shown in Fig. 3. As shown in Fig. 3, the shear adhensive strength of the coating material of Sample 1 after 7 months was kept at 135 kg/ c 2 / m. After one month after making, the coating material was applied over a prestressing steel strand having a diameter of 12.7mm at a layer thickness of 0.5 to 1.0 mm, and arranged in concrete as shown in Fig. 1. After two months, it was started to measure the coefficient of friction between the concrete and the prestressing steel strand. For comparison, a conventional unbonded prestressing steel strand which is coated with grease and then covered with polyethylene sheath was arranged in concrete, and the coefficient of friction between the concrete and the prestressing steel strand was started measuring after two months. The results were shown in Fig. 4. In Fig. 4, a zone 5 shows the result of the coating material of Sample 1, and a zone 6 shows the result of the conventional unbonded prestressing steel strand. The coefficient of friction referred to here means how much of tension applied to one end of a prestressing steel strand arranged in the concrete is lost in a length in which the tension is transmitted to the other end of the prestressing steel strand and is indicated by a loss per the applied tension per a unit length (m), and the value obtained by multiplying the value of the applied tension by the value of the coefficient of friction indicates the tension lost per a unit length. With Sample 1, in six months after making, the coefficient of friction of the coating material, is as low as that of the conventional unbonded prestressed steel strand. Therfore, it is seen that in the period of six months, applied tension was sufficiently transmitted over the whole length of the prestressing steel strand. After six months, the coefficient of friction of the coating material of the present invention steeply rose. It is seen from this result that the coating material including the curing composition cured and consequently the prestressing steel strongly adhered to the concrete by means of the coating material of the present invention. On the contrary, in the case that the conventional unbonded prestressing steel strand was used, it is seen that the coefficient of friction did not rise even after 6 months and the prestressing steel strand did not adhere to the concrete. Further, the coating material of Sample 1 was applied to the prestressing steel strands of a diameter of 12.7 mm at a layer thickness of 0.5 to 1.0 mm and the coated stands were arranged in concrete in two ways of Fig. 1 and Fig. 2. After 7 months, the pulling loads of the two strands were measured. For comparison, a prestressing steel strand uncoated with the coating material was arranged in concrete and the pulling load thereof was measured after 7 months. The result is shown in Fig. 5. In Fig. 5, the ordinate indicates the pulling load and the abscissa indicates the relative sliding amount of the prestressing steel strand to the concrete. A curve 7 shows the case of coating a prestressing steel strand with the coating material of Sample 1 and arranging it in the concrete in the way of Fig. 1. A curve 8 shows the case of similarly coating a prestressing steel strand with the coating material of Sample 1 and arranging it in the way of Fig. 2. A curve 9 shows the case of arranging a prestressing steel strand coated with no coating material in the concrete. In the case of coating the prestressing steel strand with the coating material and arranging the coated strand in the concrete in the way of Fig. 1, the maximum pulling load was 8.7 ton. In the case of coating the prestressing steel strand with the coating material and arranging the coated strand in the concrete in the way of Fig. 2, the maximum pulling load was 8.9 ton. On the other hand, in the case of arranging the uncoated strand in the concrete, the maximum pulling load was 4.9 ton. Further, an unbonded prestressing steel strand was arranged in concrete and the pulling load was measured after 7 months. The value was extremely small. It is seen from the abovementioned results that by using the coating material of Sample 1, a sufficient adhering force is obtained between the concrete and the prestressing steel strand after a predetermined time. Further, the coating material of Sample 1 was applied to a prestressing steel strand of a diameter of 12.7 mm at a layer thickness of 0.5 to 1.0 mm, and the coated strand was arranged in concrete in the way of Fig. 1. After 7 months, a bending test of this concrete beam was carried out in a way corresponding to the way defined in JIS A 1106. The result was shown with a curve 10 in Fig. 6. In Fig. 6, the ordinate indicates the bending load and the abscissa indicates the mid-portion deflection. For comparison, a beam was manufactured by arranged a prestressing steel strand and grouting it with cement milk in a way used in the conventional post-tensioning system. The result of a bending test of this beam is shown with a curve 11 in Fig. 6. Further, another beam was manufactured by using an unbonded prestressing steel strand, and a bending test of this beam was carried out. The result is shown with a curve 12 in Fig. 6. It is seen from these results that the beam manufactured by the coating material of Sample 1 has substantially the same bending strength (4.2 ton) and deflection amount as the beam obtained by grouting with cement milk used in the conventional post-tensioning system and therefore the beam using the coating material of Sample 1 is better than the beam using the conventional unbonded prestressing steel strand. In the coating material of Sample 1, furthermore, the mixing ratio of the curing accelerator was changed to 0.07, 0.10, 0.15, 0.20 and 0.25 phr, to examine the relationship between the mixing ratio of the curing accelerator and the number of days required for curing of the coating material. The result is shown in Fig. 7. Further, the shear adhesive strength of the coating material (iron / iron) at each of the abovementioned mixing ratios of the curing accelerator was measured and the result is shown in Table 1. Mixing ratio of curing accelerator ( phr ) Shear adhesive strength (iron / iron) ( kg / cm² ) 0.07 140 0.10 135 0.15 110 0.20 130 0.25 115 It is seen from Fig. 7 that by changing the mixing ratio of curing accelerator, the curing time of the coating material can be so controlled that the coating material can cure in a predetermined time in a predetermined atmosphere. Further, as shown in Table 1, the shear adhesive strength in every case is as high as more than 110 kg/cm², and the coating material in which the mixing ratio of the curing accelerator is variously changed as abovementioned has also substatially the same pulling load and a bending load as the coating material of Sample 1. Example 2 To 90 parts of an epoxy-resin of bisphenol A type (epoxy equivalents; 189, viscosity; 130 poise), 10 parts of n-butyglycizylether as a diluent, 3 parts of dihydrazide adipate powdered to be 150 mesh pass as a latent curing agent, 0.03 part of 2, 4, 6- tris (N-N-dimetylaminometyl) phenol as a curing accelerator, 50 parts of calcium carbonate as a filler and 3 parts of disparlon 6900-20X (produced by Kusumoto Kasei Co.Ltd.) as an additive were added and stirredly mixed. A coating material including a curing composition was consequently obtained.This coating material had a shear adhesive strength of 105 kg/cm² in six months after making. The relationship between the curing time and the shear adhesive force of this material, and the relationship between the mixing ratio of 2, 4, 6- tris (N, N-dimetylaminometyl) phenol as the curing accelerator and the number of days required for curing this coating material and the shear adhesive strength were examined and the results are shown in Tables 2 and 3. Curing time (months) Shear adhesive strength (kg/cm²) 3 uncured state 4 uncured state 5 18 6 105 Mixing ratio of curing accelerator (phr) Days required for curing (days) Shear adhesive strength (kg/cm²) 0.25 13 90 0.10 40 98 0.05 90 110 0.03 180 108 Example 3 To 100 parts of an epoxy-resin of bisphenol AD type (epoxy equivalent; 175, viscosity; 32 poise), 4 parts of diphenylaminosulphone powdered to be 150 mesh pass as a latent curing agent, 0.05 part of 2, 4, 6- tris (N, N-dimetylaminomety l) phenol as a curing accelerator, 35 parts of tarc as afiller, 1 part of aerosil as an additive were added and stirredly mixed. A coating material including a curing composition was consequently obtained. This coating material attained a shear adhesive strength of 165 kg/cm² in six months after making Example 4 To 90 parts of an epoxy-resin of bisphenol A type (epoxy equivalent; 188, viscosity; 130 poise), 10 parts of benzyl alcohol as a diluent, 50 parts of trac as a filler, 3 parts of BF₃ · amine curing agent (Anchor 1040 manufactured by Anchor Chemical Co.Ltd.) as a latent curing agent, 3 parts of disparlon 6900-20X (produced by Kusumoto Kasei Co.Ltd.) as an additive were added and stirredly mixed. A coating material including a curing composition was consequently obtained. This coating material attained a shear adhesive strength 140 kg/cm² in an atmosphere of 21 °C in five months after making. It is apparently seen from these results that the coating materials of Examples 2 to 4 attain the same quality as that of the coating material of Sample 1.

Claims: Use of a coating material comprising 100 parts of epoxy resin, a latent curing agent, and 0.03 to 0.5 parts by weight of a curing accelerator, the latent curing agent being one of dihydrazide, diphenyldiaminosulphone, dicyandiamide, 2-methylimidazole and derivatives thereof, and BF₃ amine complexes, the curing accelerator being a tertiary amine, the coating material taking at least three days to cure at ambient temperature, for coating a tendon for incorporation into prestressed concrete. Use of a coating material according to claim 1, wherein the curing accelerator is 2,4,6-tris(N,N-dimethylaminomethyl)phenol or N,N-benzylmethylamine. Use of a coating material according to claim 1 further comprising a diluent and a filler. Use of a coating material according to claim 1 wherein the coating material takes between three days to one year to cure at ambient room temperature. Use of a coating material according to claim 1, wherein the epoxy resin is a polyglycidyl compound which is a polyhydric phenol or a polyhydric alcohol, or a polyhydric carboxylic acid. Use of a coating material according to claim 5, wherein the polyhydric phenol is bisphenol A, bisphenol AD, TBA, hydroquinous or resorcinol, or said polyhydric alcohol is ethylene glycol or glycerine, or said polyhydric carboxylic acid is phthalic acid. Use of a coating material according to claim 1, wherein the dihydrazide is dihydrazide of adipic acid or of sebacic acid. Use of a coating material according to claim 3, wherein the filler is one of calcium carbonate, talc and silica, the coating material further comprising aerosil as an additive for dispersing and preventing precipitation of the filler. Use of a coating material according to claim 1, wherein the latent curing agent has an active hydrogen and the molar ratio of the latent curing agent to the epoxy radical of the epoxy resin ranges from 1:0.5 to 2.0. Use of a coating material according to claim 1, wherein the latent curing agent is ionic and the ratio of said latent curing agent to the epoxy resin is 0.5 to 1.0 part curing agent per 100 parts epoxy resin. Use of a coating material according to claim 1, wherein the amount of the curing accelerator present is 0.05 to 0.5 parts by weight.

Inventors: HASHIMOTO, MICHIO, HAYASAKI, KIYOSHI, KURAUCHI, MAKOTO, MINAMI, TOSHIKAZU, OHNISHI, MUTSUHIKO, SUZUKI, YOHEI
Applicants: MITSUI SEKIYU KAGAKU KOGYO KABUSHIKI KAISHA, SHINKO KOSEN KOGYO KABUSHIKI KAISHA
Application year: 1988
Main classification: C09D163
IPC codes: E04G21, E04C5, C09D5, C08G59, C09D163, C09J163