Biocidal colloidal dispersions of silica particles with silver ions adsorbed thereon

(12) Patent Specification do SE 533 902 C2

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Sweden (21) Patent application number: 0901216-2 (45) Patent granted: 2011-02-22 (41) Application generally available: 2011 -02-22 (22) Patent application submitted: 2009-09-22 (24) Maturity date: 2009- 09-22 (83) Deposit of microorganism: - (30) Priority information: - (51) International class:

C01G 5/00 (2006.01)

A01N 59/16 (2006.01)

C01B 33/14 (2006.01) (73) Patent holder: Small Particle Technology Gbg AB, Gamla Vägen 11, 272 37 Simrishamn SE

<td>(72) Inventor:</td><td>Jan-Erik Otterstedt, Simrishamn SE</td>

<td>(74) Agents:</td><td>BRANN AB, Box 12246, 102 26 Stockholm SE</td>

<td>(54) Name:</td><td>Nanoparticles of silver</td>

<td>(56) Publications cited:</td><td>US 5730995 A · US 20070009672 Al · WO 2004073400 A2 · WO 2008122131 A1 · EP 0488269 A1 · US 5651978 A · WO 2006128793 A1 · US 5651978 A</td>

(47) Summary:

The invention relates to a colloidal dispersion comprising silica carrier particles having a particle size from 3 nm to 100 nm to which silver ions have been adsorbed. The invention also relates to a method of preparing a colloidal dispersion comprising the steps of providing a silicic acid sol and adding a solution of silver nitrate to the silicic acid sol with stirring to obtain a colloidal dispersion with silver ions adsorbed on the surface of the silicic acid particles. The colloidal dispersion can be used as a biocide.

533 902

Summary

The invention relates to a colloidal dispersion comprising silica carrier particles having a particle size from 3 nm to 100 nm to which silver ions have been adsorbed. The invention also relates to a method of preparing a colloidal dispersion comprising the steps of providing a silicic acid sol and adding a solution of silver nitrate to the silicic acid sol with stirring to obtain a colloidal dispersion with silver ions adsorbed on the surface of the silicic acid particles. The colloidal dispersion can be used as a biocide.

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Nanoparticles of silver

Field of the Invention

The present invention relates to silver nanocomposites. In particular, it relates to such materials made up of nanoparticles, e.g. colloids, which have a well-controlled size and high degree of dispersion of silver. It also relates to processes for producing such materials and using them in various applications where biocidal effect is desired.

Description of the prior art

Nanotechnology is about the sciences and techniques used to design materials at the atomic level. Materials made using different types of nanotechnology have begun to be used in many areas of everyday life such as cosmetics, fabrics and clothing, sports equipment, paints, packaging, foodstuffs etc. and have been used for some time to produce catalysts for many important industrial processes. . In the future, we will undoubtedly see many more applications of nanomaterials in general and nanomaterials containing precious metals in particular.

Colloidal gold has been successfully used in the treatment of rheumatic arthritis. In vitro studies have shown that the combination of microwaves and colloidal gold can destroy fibrils and plaques associated with Alzheimer's disease. Gold nanoparticles are being investigated as carriers for drugs like Paclitaxel. In cancer research, colloidal gold can be used to label tumors for detection with SERS, Surface Enhanced Raman Spectroscopy, in vivo.

Internal surfaces of Samsung appliances, such as refrigerators and air conditioners, are coated with a layer of nanosilver that provides an overall effect against bacteria and mold. As air circulates, it comes into contact with silver ions in the coated surfaces that can counteract the airborne bacteria's respiration, interfere with their cellular metabolism and inhibit cell growth. Samsung claims that silver nanotechnology sterilizes more than 650 kinds of bacteria and that a Samsung WM1245A washing machine releases more than 400 billion silver ions that can penetrate deep into any kind of fabric, creating a protective, sterilizing layer that provides up to 99.99% disinfection plus an antibacterial effect lasting up to 30 days after washing.

Attempts are made to incorporate silver nanoparticles, which have an antimicrobial effect lasting longer than ionic silver, in a variety of medical articles such as bone cement, surgical instruments, surgical masks, wound wraps, etc.

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WO 2008/079149 A1 discloses an antimicrobial formulation for dental applications comprising colloidal silver, from about 0.01 to 2%, and colloidal copper, from about 0.05 to 10%.

WO 2008/147395 A2 claims a solid or foamed polymer compound of rubber, synthetic rubber or neoprene, or other suitable polymer containing nanoparticles of at least one metal or metal alloy of silver, gold, palladium, platinum and copper. WO 2008/024422 A2 describes the incorporation of colloidal silver into formulations used to completely or partially decontaminate surfaces that have been contaminated with chemical or biological warfare agents and methods for treating viral, bacterial and mold infections and cancerous tissue.

WO 2008/033206 A1 discloses disinfectant formulations that are harmless to humans and to foods that may contain colloidal silver. EP 2 018 839 A1 describes preservative formulations with 0.1 to 1 ppm electrolytic silver for cosmetic products.

US 2009/0013825 A1 discloses a simple method for preparing silver nanoparticles of well controlled size in a surfactant solution. The silver manoparticles are made according to the following stepwise procedure: (1) crystals of silver nitrate are dissolved in distilled water; (2) the surfactant, LABS (Linear alkyl benzene sulfonate), is added to the solution and; (3) reducing agent is added to the solution. Preferred reducing agent is hydrazine.

US 2007/0009672 A1 describes a method for preparing a nanocomposite solution comprising preparing a basic aqueous solution of colloidal silica; make an electrolytic apparatus by installing a negative electrode containing aluminum and a positive electrode containing silver in the basic aqueous solution of colloidal silicic acid; and form nanocomposites by applying voltage to the electrodes of the electrolyzer. With this device, the invention provides a method for preparing nanocomposites dispersed in a solution and, in particular, a method for preparing a nanocomposite solution which has excellent storage and heat stability and which has anti bacterial effect.

WO 2007/117087 A1 demonstrates an efficient polymer membrane for olefin transport that can separate olefins and paraffins using metal nanoparticles, especially silver, gold or copper nanoparticles as carriers to achieve more efficient transport.

WO 2008/024426 A2 describes absorbent hygiene articles for women such as sanitary napkins, tampons and disposable diapers with antimicrobial ability to minimize odors caused by body fluids. The articles of the invention have an absorbent member such as an absorbent pad which

533 902 contains an antibacterial amount of substantially immobilized nanosilver particles or particles containing silver ions, preferably enclosed in a soluble carrier such as dextran, or similar support, or a water-insoluble but water-swelling superabsorbent polymer.

WO 20081100163 discloses a method for preparing silver nanoparticles, cellulosic fibers and nanofibers containing silver; use of silver nanoparticles in the manufacture of cellulose fibers and nanofibers and wound dressings containing silver nanoparticles.

WO 2008/147427 A2 describes a colorless material comprising silver particles and water. The particles have an interior of elemental silver and an exterior of ionic silver oxide. The content of silver particles in the water is about 5-40 ppm. A preferred embodiment of the invention is a silver material comprising silver particles where more than 50% of the particles are less than 0.015 microns in size and the particles are colloidally suspended in water. The material exhibits significant antiviral properties and is effective against avian influenza viruses. Methods for manufacturing the material are described.

WO 2009/036714 A1 describes a material for the treatment of wounds containing hyaluronic acid, urea and colloidal silver.

EP 2,027,956 A1 discloses a method for producing colloidal gold which comprises a nucleation step to form colloidal particle sprouts by adding a first reducing agent to a first gold salt solution; and a growth step in which colloid sprouts grow by adding a second gold salt and a second reducing agent to the solution of colloidal sprout particles. The method characterized by performing the growth step at least once; a citrate is used as the first reducing agent and an ascorbate is used as the second reducing agent and the addition of the ascorbate in the growth step is done simultaneously with the addition of the second gold salt.

Prior art describes the preparation and use of colloids of precious metals, primarily silver, as biocides in various applications. Particle size and particle size distribution are often indicated important properties of such colloidal dispersions, although their values ​​are rarely specified. In some prior art it is claimed that it is desirable that at least 50% of the particles have a particle size less than 15 nanometers.

Prior art also describes the use of noble metal ions as biocides. It can be said that the ions in, for example, aqueous solutions of silver salts are perfectly dispersed. In such solutions, the dispersion rate of the precious metals is 100% but they can also be removed by e.g. healing from places where their biocidal function is needed and end up on plastics where their biocidal function is undesirable.

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Summary of the Invention

It is well known that silver has biocidal properties, but there is a need for a new form of silver that combines high biocidal activity with nanoparticle leaching resistance and with perfect dispersion of ions. This means that a given effect can be achieved with much less silver in the form of the material of the present invention than with silver in conventional colloidal dispersions.

It is therefore an object of the present invention to provide colloidal forms of silver, i.e. they consist of nanostarous particles, but still exhibit practically perfect dispersion of the metal. In one embodiment of the invention, silver species are adsorbed on the surface of the particles in colloidal dispersions of silicic acid. In another embodiment, silver species are adsorbed on the surface of the nano-sized particles of silicic acid powder.

Another aspect of the present invention is that colloids with significantly higher levels of silver can be prepared than is possible with conventional silver dispersions. A further aspect of the invention is that particle size and particle size distribution can be tailored to meet tight specifications. Another aspect of the present invention is that the relatively high silver content achievable facilitates formulations of many products; e.g. paints and sealants containing materials of the present invention. Another aspect of the present invention is that the process of making materials according to the present invention is simple, robust and cost effective.

It is well known that if the pH of a silver salt solution is raised to above 8 or 9, silver oxide, Ag₂Oh, out. It is therefore surprising that silver can be present in comparatively high levels, e.g. 1000-2000 ppm silver, in the materials of the invention, many of which have a pH higher than 9, without precipitation.

In addition, it is well known that soluble chlorides, e.g. in the form of a solution of sodium chloride, is added to a solution of silver nitrate and immediately a white precipitate of silver chloride is formed. On the other hand, if a solution of sodium chloride under similar conditions is added to a material of the present invention, no precipitate is formed.

Detailed description of the invention

sILICIC aCID

A suitable source for the silica particles of the present invention are commercial silica sols. Such sols are dispersions in water of silicic acid particles. The particles are uniform spheres of silica which lack internal surface

533 902 and detectable crystallinity. They are usually dispersed in an alkaline medium which reacts with the silica surface to form a negative charge. The negative charge of the particles causes them to repel each other and produce a stable product.

In some commercial products, the particle surface is modified with aluminum silicates to give the surface a fixed, pH-independent negative charge that makes the soles more stable against gelation than the soles from which they were made. Trivalent aluminum atoms have replaced some of the quaternary silicon atoms in the particle surface, forming a fixed negative charge that is independent of pH. The surface coating of Al is much smaller than that of a Langmuir monolayer.

There are also commercial silica sols where the particles have a positive charge and are dispersed in an acidic solution. The negative surface charge has been reversed by adsorption of octahedral aluminum ions such as those found in basic aluminum chloride.

The dry content depends on the particle size and ranges from less than 10% by weight of silicic acid for the smallest particles, 3 nm, to about 50% by weight of silicic acid for larger particles,&gt; 20 nm. The particle surface in silica aquasols is covered with surface hydroxyl groups, silanol groups. Stabilization of commercial silica sols is accomplished by adjusting the pH of the sol to between 8.0 and 10.0 by the addition of alkali, usually a solution of sodium hydroxide.

The sols also contain small amounts of other electrolytes such as sodium chloride and sodium sulfate.

The stability of high-silica sols is very sensitive to the presence of electrolytes. The electrolyte content can be reduced to a minimum by using ion exchange resins. The silica (-) sols used to make the materials of the present invention are commercial products or commercial silica sols modified, e.g. by treating the sun with sodium aluminate solution to create aluminum silicate sites on the particle surface, using methods well known in the industry.

Procedures and methods

Nanocomposite materials of the present invention are prepared by contacting a non-metallic support material in the form of e.g. colloidal silicic acid or silicic acid powder with a solution containing silver species. The reactants and products used in the various preparations and methods belong to the fields of colloids and colloid chemistry and due care must be taken with respect to levels of reactants and products, maintaining high electrical charge on the particles, use of good quality water,

533 902 preferably deionized water, observing the appropriate rate of addition and arrangement of the components, operating in moderate but realistic temperature ranges and having sufficient agitation to maintain stability against gelling or aggregation of reactants and products.

The concentrations of colloidal silicic acid used in the various formulations of the present invention range from 1 wt% SiO 2 or less to undiluted commercial sols which may contain 30 wt% SiO 2 or more.

Most soluble silver items can be used to make the materials of the present invention, but the preferred salt is silver nitrate

The content of the silver salt solutions used in the various preparations has been relatively low. Mostly, 0.1 molar solutions have been used but higher, e.g. 1 molar AgNC&gt; 3 ​​and 0.5 molar AgNO3, or lower levels have also been used.

The charge of metal ions in solution, usually aqueous solutions, is normally positive. Such is the case for silver which usually, but not always, forms monovalent cations in aqueous solution.

In order to achieve strong adsorption of metal ions on the surface of nanostarous carrier particles, the electric charge on the latter should be high but opposite to the charge of the metal ions.

In an environment of water, the charge of the particles in colloidal silicic acid or the particles in the silicic acid powder increases exponentially with pH and is almost 0.5 units of negative charge per nm² particle surface at pH of about 10 and at very low, 10 ' ⁴ normal electrolyte levels. Colloidal silicic acid has a local stability maximum at the zero charge point which occurs at about pH 2.0. The stability of a silica sol first decreases with pH and reaches a minimum around pH 6, after which soles enter a range of high stability between pH 8 and pH 10.5.

The surface charge of the silicic acid, like many other metal oxides, can be changed by modifying the surface in different ways. In a method where the particle surface of silica sols is modified with aluminum silicate ions, the surface receives a fixed, pH-independent, negative charge that makes the sun more stable against gelation in the presence of electrolytes and at low pH, e.g. pH 4-5, than the soles from which they were made.

An easy way to introduce aluminum silicate sites on the surface of colloidal silicic acid is to use weakly acidic cation exchange resin to remove sodium ions from the silicic acid-sodium aluminate system and thus effect the reaction of the aluminate ions with the silicic surface. In this system, the pH usually does not fall below 5, even if an excess of slightly acidic cation exchange resin has been used. An estimated amount of sodium aluminate solution to give the desired number of aluminum silicate sites per nm² particle surface is added to the slurry of silica sol and resin.

533 902

The creation of aluminum silicate sites on the surface of silicic acid is well described in the literature. Such descriptions also show that it is difficult to introduce much more than about 2 aluminosilicate sites per nm² silica surface.

The aluminum silicate sites have a negative charge that must be neutralized by counterions, usually Na⁺ions. Modification of the silica surface with sodium aluminate converts the surface into a cation exchanger.

Although adsorption of metal cations on aluminum silicate-modified silica can occur over a wide pH range, the adsorption should preferably be in the pH range where the silica sol is most stable, e.g. in the pH range from about 8 to about 10.5.

The rate at which silver salt solution can be added to the silica sol without destabilizing the sun depends on the conditions prevailing at the time of preparation. The rate of addition can be high if only the amount of salt added is virtually instantaneously dispersed throughout the sun and where the silicic acid particles are rapidly adsorbed. Indeed, it is quite surprising how robust the colloidal systems are made with the technique of the present invention. In fact, in many of the small-scale preparations it is possible to inject 0.1 M AgNO3 solution in magnetically stirred silica sols for a very short time, e.g. 10-15 seconds, without destabilizing the sun. In most laboratory scale preparations, e.g. however, for the preparation of sols containing about 500 ppm metal, longer times are used to add 0.1 molar silver salt solutions, typically 2-3 minutes, to ensure good stability to gelation or aggregation. Suns with higher silver levels may require longer addition times. Thus, a sol containing 1500 ppm silver may need an addition time of 0.1 molar silver solution of about 12 minutes. Similar time scales apply to preparations on a larger scale, provided that the agitation is as effective as in the preparations on a smaller scale.

A sun with a given content of silver can be prepared in different ways. In one method, a certain amount of silver nitrate solution is added to a silica sol with specified values ​​of particle size and silica content. In another method, the same amount of silver nitrate solution is added to a sol of the same particle size but higher, e.g. four times higher silica content. The content of silver is the same in the two suns, but the concentration of silver on the particle surface in the former sun is higher - four times higher - than in the latter sun. Thus, a material of the present invention with a given silver content can be made by combining high content of particles, i.e. high silica content, low concentration of silver on the particle surfaces or by combining a high surface concentration of silver with low silica content.

533 902

The content of silver in the sols of the present invention ranges from less than 0.1% SiO₂ to 50% SiO₂, preferably 0.5 - 30% SiO₂, or more preferably 1-25% SiO₂.

Prior art describes the preparation and use of colloidal forms of precious metals, especially colloidal silver, as biocides in various applications. Particle size and particle size distribution are often described as important properties of such colloidal dispersions, although they are rarely specified. In some prior art it is claimed that it is desirable that at least 50% of the particles have particle sizes less than 15 nanometers. When noble metal nanoparticles are used as biocides, only metal atoms on the surface of the particles can contact and interact with microbes of various kinds. Metal atoms in the interior of the particles do not have access to the environment outside the particles and therefore have no biocidal activity. Let n_s and n_t enter the number of surface atoms and the total number of atoms, e.g. noble metal atoms. Ratio ns / n_t is called the degree of dispersion of the precious metal and is a very important property of precious metals in applications, e.g. many catalytic or biocidal applications, where their performance depends on the number of atoms they are exposed to their surroundings. The degree of dispersion decreases rapidly with the particle size. In the case of e.g. Thus, silver nanoparticles decrease the dispersion rate from about 85% to about 30% as the particle size increases from 1 nanometer to 5 nanometers. For 15 nanometer particles, the dispersion rate is less than 10%, indicating that more than 90% of the particles are inactive in the interior of the particles.

The concentration of silver species on the surface of the ultimate particles of the materials of the present invention is made in the range of from about 0.005 to more than 5 silver species per nm². The term silver species means silver ions, silver atoms or silver oxides.

The silica sols of the present invention can be dried to a powder. According to one method, water is simply removed by blowing air over a thin film of the sun or by vacuuming the sun. In another method, the interaction between the particles in sols of the present invention can be reduced by adjusting the pH to between 3 and 5, preferably to between 4 and 5, by ion exchange and / or the addition of strong acid before water is removed from the system by drying in an air stream. or vacuuming. Powders of the present invention can also be prepared by treating commercial amorphous silicic or amorphous aluminum silicate powder with silver nitrate solution to achieve the desired concentration of silver on the primers or ultimate particles that the powder consists of and removing water by drying in an air stream or vacuum.

The invention is described in more detail but is not limited by the following embodiments.

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Example

In Examples 1 through 31 of Table 1, the indicated amounts of 0.1 molar silver nitrate solutions were added to 50 g of magnetically stirred silica sols during the times also indicated in Table 1.1. Examples 32 to 35 made larger amounts of sol. In Example 32, e.g. 1000 g of starting sun. Columns 2 to 4 indicate particle size, content of S1O2 in the starting sun and the number of aluminum silicate sites per nm, respectively.² particle surface. Columns 5 and 9 show the pH of the sun before and after the addition of silver nitrate solution. In the first 30 examples except Example 19, silver nitrate solution was added with a plastic pipette. In Examples 19 and Examples 32 - 35, silver nitrate solution was added with a Watson pump.

Examples 36 and 37 show that silver nitrate solutions with high silver content can be used to make materials according to the present invention.

Example 36

6.0 g 0.5 M AgNO₃ - solution was added with plastic pipette to 50 g of 12 nm silica sol with an aluminization rate of 1.6 Al per nm² particle surface and containing 15 wt% SiO₂ for 7 minutes and with magnetic stirring. The concentration of Ag in the silver-coated silica sol was 5785 ppm.

Example 37

7.0 g 1.0 m AgNO₃ solution was added with plastic pipette to 50 g of 5 nm silica sol with an aluminization degree of 0.7 Al per nm² particle surface and containing 5% by weight SiO₂ for 4 minutes and with magnetic stirring. The concentration of Ag in the silver-coated silica sol was 1500 ppm.

The following example describes modification of the silica surface by treating silica sols with sodium aluminate solutions.

Example 38 The pH of a 22 nm sol containing 20% ​​SiC&gt; 2 was adjusted to 8.5 with a strongly acidic ion exchange resin in the hydrogen form. 2500 grams of this sol was placed in a beaker and 9.12 g of sodium aluminate solution (made by diluting 2,914 g of NaAlO₂ in 6.205 g of deionized water) was added dropwise to the vortex of the strongly stirred silica sol for about 25 minutes. The resulting sun had a pH of 9.5. Assuming that all added aluminum forms aluminum silicate seats, there would be 0.3 such seats per nm² silica surface. The procedure can be repeated and the number of aluminum silicates per nm² can be increased to about 2 in increments of preferably 0.3 seats per repeat.

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The following two examples show the unique properties of the metals in the colloidal nanometallic composites of the present invention.

Example 39

The sol of Example 26 was diluted to 100 ppm Ag. 0.1 m AgNO₃ - solution was diluted to 100 ppm Ag.

To each of the solutions were added 5 drops of 0.1 M NaCl solution. A whitish precipitate formed immediately in AgNO₃ - the solution but the sun was not affected by the addition of NaCl.

Example 40

The sun in Example 32 looks like a water-clear solution with a slightly dark hue. The silver content is 1000 ppm and the pH is 8.65. In comparison, when silver nitrate was added to water of pH 8.65 so that the solution also contained 1000 ppm silver, a precipitate formed immediately.

The following two examples show the biocidal effect of products of the present invention.

Example 41

The sol of Example 28 and 0.1 M AgNO₃ solution diluted to 1000 ppm Ag was used in this example. Slices of French bread from a local baker were used as a substrate for mold growth.

1st Bread plate was brushed on all sides with the sun containing 1000 ppm Ag

2nd Bread plate was brushed on all sides with 0.1 m AgNO₃- solution diluted to 1000 ppm Ag

3rd Bread slice was untreated

The bread slices on a plate were placed in a plastic bag which in turn was placed in a glazed porch where the temperature varied between 20 and 35 ° C during the day. Figure 1 shows the bread slices after three days in the warm and humid atmosphere. The untreated bread slab is heavily infested and the slab appears to be completely invaded by mold. Treatment with AgNO₃ - solution gives some protection but the number 2 disc also seems to be overflowing with mold. Although mold has gained a foothold on some spots on the surface of the disc treated with the sun according to the present invention (disc 1 in the picture)

Example 42

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The sun in Example 20 was brushed on roof tiles covered with green moss. At first contact with the sun, the moss instantly blackened - see picture 2.

Example 43

The sun of Example 25 could easily be blended into commercial lacquers and colors, e.g. Nanofloor Refresher from Nanosol AB, Gothenburg, Alpina Paint V, a matte, white outdoor paint with an acrylic binder, from Alpina AB, Gothenburg, Sweden, to stable formulations containing 100 ppm silver.

The tests show that the materials of the present invention can be prepared as stable sols with silicon content in the range of less than 1% SiO₂ to more than 25%, and concentration of silver species in the material from less than 5 ppm to more than 5,000 ppm Ag.

The materials of the present invention can also be prepared as powders consisting of silica primers whose surface contains silver species in amounts from about less than 5 to more than 10,000 ppm Ag.

The materials of the present invention are effective biocides. They can be used as they are or mixed in commercial paints and varnishes into stable formulations with biocidal properties.

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patent Example

<td>Exempe 1</td><td>particle size, nm</td><td>Silica content. %</td><td>Aluminum silicate sites per nm²</td><td>pH of the starting sun</td><td>Amount 0.1 M AgNOs₃solution 9</td><td>Addition time, minutes</td><td>Conc. of ads. metal in the sun, ppm</td><td>pH of composite sol</td>

<td> 1</td><td> 12</td><td> 5</td><td> 0</td><td> 9.88</td><td> 2.55</td><td> 2.5</td><td> 500</td><td> 9.61</td>

<td> 2</td><td> 12</td><td> 10</td><td> 0</td><td> 9.85</td><td> 5.10</td><td> 5</td><td> 1000</td><td> 9.55</td>

<td> 3</td><td> 12</td><td> 15</td><td> 0</td><td> 9.85</td><td> 7.60</td><td> 8</td><td> 1500</td><td> 9.48</td>

<td> 4</td><td> 12</td><td> 30</td><td> 0</td><td> 9.90</td><td> 2,51</td><td> 2.5</td><td> 500</td><td> 9.82</td>

<td> 5</td><td> 22</td><td> 5</td><td> 0</td><td> 9.52</td><td> 2,55</td><td> 2.5</td><td> 500</td><td> 9.08</td>

<td> 6</td><td> 22</td><td> 10</td><td> 0</td><td> 9.50</td><td> 5.10</td><td> 5</td><td> 1000</td><td> 8.91</td>

<td> 7</td><td> 22</td><td> 15</td><td> 0</td><td> 9.45</td><td> 7.60</td><td> 8</td><td> 1500</td><td> 8.82</td>

<td> 8</td><td> 3</td><td> 7</td><td> 0.6</td><td> 9.35</td><td> 2.51</td><td> 2.5</td><td> 500</td><td> 9.04</td>

<td> 9</td><td> 5</td><td> 1</td><td> 0.7</td><td> 9.72</td><td> 2 55</td><td> 2.5</td><td> 500</td><td> 8.56</td>

<td> 10</td><td> 5</td><td> 3</td><td> 0.7</td><td> 9.76</td><td> 5.10</td><td> 5</td><td> 1000</td><td> 8.67</td>

<td> 11</td><td> 5</td><td> 5</td><td> 0.7</td><td> 9.79</td><td> 2.48</td><td> 2.5</td><td> 500</td><td> 9.34</td>

<td> 12</td><td> 5</td><td> 15</td><td> 0.7</td><td> 10.02</td><td> 2.54</td><td> 2.5</td><td> 500</td><td> 9-68</td>

<td> 13</td><td> 7</td><td> 5</td><td> 1.0</td><td> 10.61</td><td> 2.55</td><td> 2.5</td><td> 500</td><td> 9.77</td>

<td> 14</td><td> 7</td><td> 10</td><td> 1.0</td><td> 10.12</td><td> 2.55</td><td> 2.5</td><td> 500</td><td> 9.76</td>

<td> 15</td><td> 7</td><td> 15</td><td> 1.0</td><td> 10.02</td><td> 2.54</td><td> 2.5</td><td> 500</td><td> 9.68</td>

<td> 16</td><td> 7</td><td> 10</td><td> 1.0</td><td> 10.61</td><td> 5.10</td><td> 5</td><td> 1000</td><td> 9.53</td>

<td> 17</td><td> 7</td><td> 15</td><td> 1.0</td><td> 10.61</td><td> 7.60</td><td> 8</td><td> 1500</td><td> 9.34</td>

<td> 18</td><td> 12</td><td> 15</td><td> 1.6</td><td> 11.35</td><td> 15.2</td><td> 12</td><td> 2518</td><td> 9.58</td>

<td> 19</td><td> 12</td><td> 27.1</td><td> 1.6</td><td> 11.16</td><td> 30.0</td><td> 200</td><td> 4080</td><td> 9.59</td>

<td> 20</td><td> 12</td><td> 10</td><td> 1.6</td><td> 10.81</td><td> 5.10</td><td> 0.1</td><td> 1000</td><td> 10.18</td>

<td> 21</td><td> 12</td><td> 27.1</td><td> 1.6</td><td> 10.77</td><td> 0.51</td><td> 1</td><td> 100</td><td> 10,77</td>

<td> 22</td><td> 12</td><td> 27.1</td><td> 1.6</td><td> 10.77</td><td> 2.55</td><td> 2.5</td><td> 500</td><td> 10.70</td>

<td> 23</td><td> 12</td><td> 27.1</td><td> 1.6</td><td> 10.77</td><td> 5.10</td><td> 5</td><td> 1000</td><td> 10.64</td>

<td> 24</td><td> 22</td><td> 5</td><td> 0.7</td><td> 9.22</td><td> 2.55</td><td> 2.5</td><td> 500</td><td> 8.81</td>

<td> 25</td><td> 22</td><td> 10</td><td> 0.7</td><td> 9.43</td><td> 5.10</td><td> 2.5</td><td> 1000</td><td> 8.69</td>

<td> 26</td><td> 22</td><td> 15</td><td> 0.7</td><td> 9.50</td><td> 7.60</td><td> 2.5</td><td> 1500</td><td> 8.65</td>

<td> 27</td><td> 22</td><td> 5</td><td> 1.5</td><td> 10.61</td><td> 2.55</td><td> 2.5</td><td> 500</td><td> 9.97</td>

<td> 28</td><td> 22</td><td> 10</td><td> 1.5</td><td> 10.61</td><td> 5.10</td><td> 5</td><td> 1000</td><td> 9.75</td>

<td> 29</td><td> 100</td><td> 20</td><td> 1.5</td><td> 11.12</td><td> 2.55</td><td> 2.5</td><td> 500</td><td> 9.67</td>

<td> 30</td><td> 100</td><td> 25</td><td> 1.5</td><td> 11.12</td><td> 5.10</td><td> 5</td><td> 1000</td><td> 9.52</td>

<td> 31</td><td> 5</td><td> 4</td><td> 0.7</td><td> 9.80</td><td> 5.56</td><td> 3</td><td> 1200</td><td> 8.52</td>

<td> 32</td><td> 12</td><td> 10</td><td> 0.8</td><td> 10.32</td><td> 50.00</td><td> 50</td><td> 500</td><td> 9.76</td>

533 902

<td> 33</td><td> 5</td><td> 3</td><td> 0.7</td><td> 9.76</td><td> 50.0</td><td> 52</td><td> 1000</td><td> 8.65</td>

<td> 34</td><td> 12</td><td> 3</td><td> 1.6</td><td> 10.87</td><td> 15.3</td><td> 20</td><td> 1434</td><td> 8.21</td>

<td> 35</td><td> 12</td><td> 3</td><td> 1.6</td><td> 10.87</td><td> 52.8</td><td> 113</td><td> 1616</td><td> 8.61</td>

533 902