Patent Application
20160214909
The invention relates to a method and apparatus for removal of salts from porous materials, such as brick/cement/concrete, and for removal of chloride ions from reinforced concrete.
A common way of removing salts from materials is to flood the surfaces with plain water in order to wash away the salts. The transport of the ions from the material will then be considered as the transport of ions towards liquid having lower concentrations of the ions in question in accordance with the laws of thermodynamics, such as Fick's law of diffusion, the Nernst-Plank equation, which is an extension of Fick's law of diffusion as it also includes movement of ions in electric fields, or the basic Einstein equations. These laws consider the movements of ions/particles based on their electric charge in electric fields, the potentials of the particles, the viscosity of the liquid, etc.
These laws apply when ions are dissolved in liquids, but apply to a lesser extent in the case of salt solutions in porous materials where the pores are only partly, and often barely, filled. The pore water consists always of salt solutions of varying ion concentrations locally in the pore system, and large quantities of the ions are fully or partially chemically bound in the material in the form of different salts (Friedel salts or other salts).
Other methods for extraction of salts are based on electrolysis between an external anode and the use of reinforcement or an installed rod on the opposite side as cathode. Electrochemical methods should be called ion extraction as the negative ions move towards the anode external to the material, whilst the positive ions are drawn towards the reinforcement. The free ions will move towards anode and cathode according to their electric charge.
Use of external anodes requires the anodes to be surrounded by ion-containing anode material, which means a great deal of installation and clean-up work, and also results in pollution. Moreover, the method requires the work area to be closed off, as the anode material may be hazardous to health.
The electrochemical methods are based on an anode being placed in inert material on the concrete surface. The anode is covered with a wet mass that acts as electrolyte for passing electricity from the anode into the concrete. A typical electrolyte is a liquid or cellulose material having electrolytic properties. Alternatively, ion-containing clays are used against the concrete surface, the anode being placed in the surface of this mass. Direct current is then applied between the anode and the reinforcement. The negative chloride ions migrate towards the positive anodes on the concrete surface.
If the electrolyte is not a liquid, the anode material must be wetted at regular intervals to prevent it from drying out, as the water molecules will migrate away from the anode towards the reinforcement.
WO 8908170 from the same inventor is an example of such a method where the intention was to carry out cycles of wetting by passing water along a mat placed on the concrete surface so as to wet the concrete. The liquid was then to be pumped out and dry hot air was to be pumped through the mat to dry out the concrete surface so that salts were drawn towards the surface. This was to be done in cycles in order to draw chloride ions near the surface out into the liquid, which was then drained off. The space between the sheeting and the concrete was then to be filled with an electrolyte. A voltage was then to be applied between the anode located in the mat and the reinforcement. The chloride ions near the reinforcement were then to migrate across the surface and out into the electrolyte.
The existing techniques for removing chloride ions/other ions require the anode on the concrete surface to be covered with electrolyte in the form of liquid or a mass having electrolytic properties. This made the methods very work-intensive and physically demanding.
The electrolyte material that has to be flushed away will be environmentally harmful, resulting in requirements having to be made with respect to collection and delivery to an approved disposal site.
Brief Description of the Invention, Salt Extraction and Removal of Chloride Ions
The present invention relates to a method and equipment that both carries salts (anions and cations) to the surface of porous materials and moves negative chloride ions away from the reinforcement in reinforced concrete structures.
The method uses only water, water vapour and air and causes no pollution. The invention relates to a method for transporting salts from the outermost 0-100 mm of porous materials towards and to the surface. The method utilises movements of ions in the pore water of the material, when salts pass from a weak solution to a higher concentration and into crystals and back. The method can be used to remove harmful salts, anions and cations, from porous building materials, as for instance concrete, plaster, mortar and masonry, such as clay brick and natural stone, with no embedded reinforcement, and to remove aggressive chloride ions from reinforcement in reinforced concrete structures.
The basic idea of the invention is that ions, which become an integral part of salts when their concentration increases, will move towards the evaporation zone in and on the surface. When the concentration of salts reaches saturation level in the evaporation zone, different salt crystals will be formed depending on the amount of crystal water that is still bound to the salt. Formation of salt crystals is completely dependent on the relative humidity in the surrounding air having a relative humidity below the equilibrium moisture content of the salt in question. If this is not the case, the salts will not release their crystal water and thus also not develop crystals which are crucial for the transport of further ions to the evaporation zone. The method is therefore based on it being possible to control the relative humidity in the air and the temperature so as to obtain optimal evaporation in relation to the ability of the crystal to release crystal water, and so that the drying out is not so intense that the film of water in the pores disappears since the ions move in this film of water.
That salts are formed on the surface means that the concentration of both positive and negative ions will increase on the surface. On later supply of moisture and electrolysis, these ions will be incorporated as electrolyte according to another aspect of the invention.
According to an exemplary embodiment, the invention can be executed using equipment that is shown in
The invention is based on the utilisation of knowledge regarding the equilibrium moisture content of the salts, what happens when water evaporates from a salt solution and the phase transitions through a weak solution towards a stronger solution, saturation, deposit of different salt crystals and the growth of such crystals.
If there is a porous material containing different salts and it is desired to remove/reduce parts of a specific salt, this can be done by controlling the relative humidity levels (RH) and temperature levels in the air under the sheeting.
The Effects
The properties of salts have different effects on materials.
Chloride salts in concrete lead to corrosion of reinforcement and to extensive damage during freezing/melting cycles in the course of late autumn, winter and early spring. Chloride salts are presumed to penetrate into concrete by diffusion/migration on the basis that different salt concentrations on the surface and deeper inside the concrete are sought to be evened out. Laws of thermodynamics are used to explain and estimate chloride penetration.
Other salts such as NaSO4 break down the structure of concrete and stone and may result in extensive damage to concrete, plaster and stone structures. It may therefore be desirable to reduce the content of the ions that form NaSO4.
In fields of science other than concrete technology and construction engineering, it is acknowledged that salts are transported over distances dissolved in water, in order then to accumulate where water evaporates, leaving an increased concentration of salts.
Examples of natural salt migration include:
The present invention manipulates salts in porous materials to migrate towards the surface by regulating relative humidity and temperature such that phase transitions occur from solution to crystals on and in the surface of salt-containing materials. The amount of different ions in a solution and the relative humidity determine what salts can be formed when water evaporates from the solution. For example, NaCl has an equilibrium moisture content at about 73% relative humidity and will not crystallise before the humidity in the air comes below 73% and the concentration of NaCl on the surface exceeds the saturation of NaCl in the solution. CaCl2 has an equilibrium moisture content at around 33% relative humidity. That means to say that calcium chloride will not crystallise before the relative humidity in the surrounding air comes below about 33%.
According to own experiments with a concrete bar standing with only one surface in a salt solution, surrounded by air having about 33% RH, evaporation from the concrete surface will result in a mixture of NaCl and CaCl2 working its way up along the concrete bar, and NaCl will crystallise some distance above the surface, whilst the CaCl2 solution will work its way further up along the bar until an incipient crystallisation of CaCl2 is seen some centimetres further up. The whole concrete bar appears wet also higher up than the NaCl crystals. When the moisture level is lowered to well below 33% RH, CaCl2 will be crystallised several centimetres above the crystals of NaCl.
The same concrete bar placed in plain water will be subjected to all evaporation in the water surface and will not appear to be moist up along the bar.
This form of salt migration will be many times faster than a normal migration through plaster and concrete, which is said to follow Fick's second law.
The method is characterised in that moistening or wetting takes place by water-saturating the air to 90-100% RH, advantageously 95-100%, and preferably up to and including 100% RH, whilst increasing the temperature. Air having 100% RH contains about 17 g of water at 20 degrees Celsius. If the temperature is raised to about 30° C. and 100% RH is obtained, the water volume per m3 will be over 50 g. When hot water-saturated air meets colder concrete or plaster surfaces, water will condense within the sheeting and on the material surfaces.
When the deposited salts are subjected to higher air humidity, they will draw moisture to themselves, but not return to their original position in the material. The method is characterised by utilising movement of salts in the processes from solution to solid (crystals).
Salts in a porous material can be manipulated to move towards the surface by optimising drying out at the surface and immediately therebelow by regulating relative humidity and temperature in surrounding air and in the material. Salts that are deposited on the surface or have moved further out in the material will draw back slightly into the material if the surface is wetted again (5-10 minutes) by supplying water-saturated air to the surface.
The invention is characterised in that the surface is subjected to wetting with water-saturated, hot air. The surface and the outermost layer is subsequently dried using dry air, with controlled humidity from 20%-1% RH, more advantageously from 10%-1%, and preferably down at 1% RH. Evaporation of water from the surface and immediately below the surface results in salts also further inside the materials migrating towards the evaporation zone and salts accumulating on and in the surface. When this process has been repeated a number of times, so much salt will be accumulated in the surface that it must be brushed off or flushed away using water.
If the material contains steel reinforcement or other electrically conducting materials that may corrode, the salts that are drawn to the surface may be used as electrolyte, and by using a rectifier and point anodes, a small rectified voltage can be applied between the anode and the reinforcement. The anode is configured such that its surface against the material surface covers less than 10% thereof. The conducting anode material is packed in a hygroscopic plastic mass in order to obtain electrical connection to the concrete surface. With oversaturated air under the mat, sufficient ions will be drawn out of the material and leached out in the anode material. An increase in the amount of free ions in the anode material will result in an increase in the passage of current and negative chloride ions will be drawn away from the reinforcement. The salts that are drawn out in the surface and towards the anode material are dissolved in water and thus form an electrolyte that is captured by the anodes and remains between anode and concrete.
When sufficient amounts of ions have been drawn out of the concrete to the anode, a constant voltage may be placed on the anode, whilst drying and wetting is repeated until the desired chloride level is reached.
The aforementioned process is repeated until the desired chloride level in the concrete cover is obtained.
This patent application does not utilise a supplied electrolyte in the form of liquid or wet paste. The inventive method uses only air and water vapour. This makes it possible to effect drying out of the surface without having to remove electrolytic liquid from the surface.
The method utilises only water vapour, and the electrolytic properties are supplied by using the ions that are drawn out of the building material through the cyclic process of wetting and drying.
This method avoids the use of environmentally harmful electrolytes that have to be removed.
The equipment for this method can therefore be installed without the use of heavy machinery and requires minimal cleaning after treatment.
Use of the method will also prompt a better understanding of the mechanisms that result in chlorides penetrating into concrete and of why damage occurs in concrete, plaster and stone when chloride salts and other salts are present on and in the concrete.
The invention will be described in more detail with reference to the figures, wherein:
As shown in
Hoses and pipes 18 are installed as shown, such that both an air humidifier 14 and an air dryer 16 are connected to the sheeting as shown. Valves 20 are able to regulate airflow, as indicated by the arrows 22 and 24.
The dryer and humidifier must be operated alternately. The surface is saturated with water from the water vapour from the air humidifier, and is dried off using dry air from the air dryer. Arrow 26 represents evaporation of water from the material surface. Arrow 28 represents direction of travel for salts during the drying process.
Salt crystals 30 are formed on the surface 10. Humidity sensors 29 are drilled into the material to be able to measure relative humidity inside the material.
Another exemplary embodiment is shown in
According to another exemplary embodiment, the anode is a line anode 38 of inert anode, packed in a hygroscopic anode material.
The invention will now be described in more detail by means of examples of various ways in which the method can be carried out.
A material contains a mixture of CaCl and NaCl. It is desired to remove/reduce the NaCl content. In this case only an air humidifier and dryer with heating element are used.
A cycle may be:
If it is desired to move CaCl towards the surface, the relative humidity within the sheeting should be between 15 and 25% RH and the temperature 30-50° C.
It may now be elected to remove the sheeting and brush away NaCl crystals or to carry out a new wetting with water vapour as indicated in point 1.
Cycles of water-saturated air and drying with hot air having low relative humidity are repeated until the desired salt level in the surface has been obtained.
Table 1 shows ranges for relative humidity and temperature that are to be utilised when drying different salts. It can be seen that the solubility of individual salts varies greatly with temperature. As shown above, it may therefore be advantageous to lower the temperature towards the end of the drying periods, so that the solubility is reduced and further salt crystals can be precipitated as long as the solution in the surface is saturated. The numerical ranges mentioned are to include all intermediate ranges, e.g., 60-70 is to include 60-69, 55-65, etc.
It is important that the pores in the concrete do not dry completely as the free ions move in water films inside the pores. If the water dries up completely, the salt migration will stop.
It is desired to remove chloride ions from a reinforced concrete structure.
The point and/or strip anodes are placed within the sheeting as shown in
Point 1 wetting and point 2 drying, see Example 1, are run a desired number of times to generate salts on the surface and on the hygroscopic anodes. When, after wetting, a sufficient amount of free ions is formed on the concrete surface and on the anodes, the rectifier is switched on. A voltage of between 5 and 20 volts can be applied, depending on how much uncertainty there is as to the occurrence of hydrogen production and hydrogen embrittlement on the surface of the reinforcement. Moist air can be supplied continuously to prevent the anodes from drying out, or the rectifier may be run at constant voltage until the anodes are so dry that current does not pass between the anodes and the reinforcement.
Voltage between anode and reinforcement may be left on for a total of from 24 hours to 48 hours. Then the salts that have gathered on the surface can be brushed off, and points 1 and 2 as mentioned above can be carried out before a new period of applied voltage between anode and reinforcement is run.
It may also be elected to supply moisture (water vapour) continuously in the period of applied voltage. Nevertheless at some point in time new, free ions must be produced for the electrolyte. The processes are run until the desired level of chloride ions at the reinforcement is obtained.
Testing of the Method
The object of the test is to document that anions and cations inside a material move towards the surface when we subject the surfaces to the cyclic variations of temperature and relative humidity as described in our patent application. As chloride ions constitute a major part of the reason why embedded iron corrodes, we give weight to documentation of changes in the chloride content. A change in the amount of others ions in pore water can be documented, but this is more complicated to do.
We also wish to draw out both anions and cations to reduce the danger of other degradation mechanisms such as freezing/melting damage, alkali reactions and other mechanisms that can be related to free ions in the pore water.
Test Set-Up
Concrete blocks as shown in
The concrete blocks are placed on small supports, such that the salt-containing liquid covers the whole of the underside and about 10 mm up along the sides of the concrete block.
A plastic sheet where a hole has been cut in the plastic in an area on top of the concrete blocks is then placed over the salt vessel and over the concrete blocks. The plastic is then glued to the concrete surface around the hole so that the concrete in the hole is exposed to the air in the room. The plastic was then glued to the edges of the salt vessel.
Thus, we have a concrete bock partially submerged in a chloride salt solution with an opposite concrete surface exposed to air where we can regulate temperature and humidity.
Locally on the concrete surface, we used a grout to delimit an area of about 120×120 mm to which we were able at intervals to supply moisture using water vapour. The other concrete surface was then exposed to air having a temperature varying between 20-35° C. and relative humidity down at about 30-33%.
In addition, we have performed chloride measurement in a reference concrete stored at ordinary room temperature.
An outline of a reinforced concrete block with added sodium chloride, which is then placed partially submerged in a salt solution, is shown in
Results after different external influences, including effect according to our application.
Cyclic wetting and drying according to the application
The small area of 120×120 mm was then subjected to the treatment that is covered by our patent application.
After about 15 cycles of rapid wetting and slow drying with low relative humidity level in the air. Includes brief flushing of the surface between each cycle.
Drying in a dry environment (stable drying)
A concrete sample with added sodium chloride that is partially immersed in a salt solution and where the opposite surface is subjected to constant drying.
Ordinary Room Temperature
A concrete sample with added sodium chloride that is stored in stable room temperature and relative humidity.
A graphical presentation of chloride content at depths of 0-5 mm, 5-12 mm and 12-20 mm after different exposure, is shown in
In addition to measuring changes in chloride content at different depths, we have also measured electrical conductivity in the surface, on wetting with water vapour after a fairly long period of drying. Conductivity is then measured along a surface where two metal rods are pressed down against the surface. The conductivity is measured using alternating current of about 1000 Hz applied voltage.
It can then be seen that the surface with high chloride content takes up moisture quickly and rapidly gives good electrical conductivity in the surface.
A surface with reduced chloride content takes up moisture slowly and it takes a long time for the conductivity to increase.
The concrete block that is stored at room temperature takes up moisture as before, and increased conductivity on wetting with water vapour lies between the aforementioned surfaces.
This is also a strong indication that the amount of free ions in the concrete surface has been reduced by our treatment of wetting and drying.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/IB2014/064980 | 10/1/2014 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 61885526 | Oct 2013 | US |
