Halogen free hardeners for waterglass

1. 2. 2.1.

INTRODUCTION ........................................................................ 2 THE USE OF HARDENERS FOR WATERGLASS................... 4 Hardeners Production and mechanism ................................... 4

2.2. Waterglass bonded masses and mortars ................................... 4 2.3. Advantages of phosphate hardeners .......................................... 5 3. 3.1. 4. 4.1. 4.2. 4.3. 5. 5.1. 5.2. 5.3. 5.4. 6. 6.1. OUR PRODUCT RANGE OF HARDENERS............................. 6 Product data of our hardeners.................................................... 7 WATERGLASS AS BONDING AGENT .................................... 9 Waterglass.................................................................................. 9 Types of waterglass ................................................................. 11 Speed of dissolution of waterglass........................................... 12 SAMPLE APPLICATIONS....................................................... 13 Powder type sodium silicate with FABUTIT 748 ...................... 13 Liquid sodium silicate with FABUTIT 748................................. 14 Liquid potassium silicate with FABUTIT 758............................ 14 General information .................................................................. 15 TESTS ...................................................................................... 16 Determination of the cold pressure strength of mixes and mortars based on waterglass.................................. 16 6.2. Determination of the acid resistance of mixes and mortars based on waterglass.................................. 16 6.3. Determination of the water resistance of mixes and mortars based on waterglass.................................. 17

1. INTRODUCTION

Today the most common opinion of many people is, that alchemists were fools, which tried to produce gold from anything, or which are engaged in the transformation of any matter. In reality today alchemistry is known as the beginning of the modern chemistry and technology, which tried to examine many raw materials and elements, like phosphorus and oxygen, as well as liquor silicum, the waterglass.

Waterglass is used in several industries in a manifold way. The hardening of waterglass is caused by CO2 from the air, by organic hardeners or special phosphates. The hardening of waterglass just by carbonic acid lead to a hardened surface of the mass. This massive layer then blocks the penetration of carbonic acid and stops the further hardening of the mass below. A complete hardening is nearly impossible. The use of organic hardeners, like silicofluoride is sensitive, because of the formation of hydrofluoric acid in contact with other acids. Such hardeners are not sustainable with the environment and they do not comply with the rules of hazardous goods.

Special phosphate, especially polymer aluminium phosphates , allow the controlled hardening of waterglass bonded masses and are environmentally friendly products.

During the technical development of waterglass based systems, waterglass and phosphate were combined to produce manifold used materials and products with a lot of future potential.

The system based on phosphate hardener and waterglass is able to bind nearly any material together. On the behalf of the acid and water resistant properties of such materials it is not surprising that such systems combined with suitable fillers are used in many applications like:

- Joint fillers - Silicate adhesive - Silicate plaster - Acid resistant mortars - Inorganic foams - Binder for fine particles - Insulating boards and materials - Binders for refractories

2. THE USE OF HALOGEN FREE HARDENERS

2.1. HARDENERS PRODUCTION AND MECHANISM

Hardeners for waterglass are produced by drying salt solutions of phosphoric acid. The reaction between the aluminium oxide and phosphoric acid for example is a neutralisation one, varying by the degree of condensation and the ratio of P2O5 and Al2O3. This leads to different reactive hardeners. In the alkaline environment of the silicate this reaction is reversed and it results in the formation of silicic precipitation products and zeolithic structures. Reacting with the hardener, the precipitation

products of the silica acid will develop a form of network as well as a polysilica gel and zeolith phases. The gel is supported by the hardener to form a network and to form water and steam resistant mixes. Waterglass can also be hardened by carbonic acid CO2. But this reaction leads to the formation of mixes, which are easily destroyed by water.

2.2. WASSERGLASS BONDED MASSES AND MORTARS Waterglass with a molar ratio of 1,0 3,5 is preferably used for the production of mortars and masses. Phosphate products such as FABUTIT are commonly used to harden such masses and mortars. The reaction of the hardener with the silicate leads to a network of silica acid particles to form a polymeric silicate structure. With FABUTIT hardened masses and mortars feature high water and acid resistance. The hardened masses and mortars show a high pressure strength. The reaction between hardener and waterglass is a chemical process. The reactivity of the hardener and the molar ratio of the waterglass do have an important influence on the setting time and physical properties of the final masses and mortars. Basically, waterglass with a low molar ratio produces masses and mortars with higher strength. The lower the molar ratio of the waterglass, the higher the alkalinity of the waterglass and the higher the liquefaction effect on the ceramic mix. This will lead to masses and mortars with a lower water content and a lower shrinkage.

2.3. ADVANTAGES OF PHOSPHATE HARDENERS

Phosphate hardeners are tested as to on whether they are sustainable with the environment . They are made of inorganic raw materials. Those phosphates are typically water insoluble, they do not contain any organic material and are non hazardous products. Contrary to other hardener systems for waterglass, as for example silicofluoride, phosphates do not contain fluorine or other halogens. These products are well known for the formation of hydrofluoric acid in contact with other acids. Such hardeners are not sustainable with the environment and they do not comply with the rules of hazardous goods.

Phosphates are mainly powder products. An easy mixing with other raw materials are is possible to form ready prepared powder formulations, used as masses and mortars. The required amount of water is added on site. The suspension hardeners, which are an exception, as they allow to work with fluid components.

3. OUR PRODUCT RANGE OF HARDENERS

STANDARD

FABUTIT 305

Hardener for lithium silicates

FABUTIT 588

Accelerated hardener for potassium silicates

FABUTIT 624

Accelerated hardener for sodium silicates

FABUTIT 748

Hardener for sodium silicates

FABUTIT 758

Hardener for potassium silicates

SPECIALITIES

FABUTIT 320

Modified hardener for sodium silicates with improved water resistance and high pressure strength

FABUTIT 574

Modified hardener for potassium silicates with improved water resistance and high pressure strength

FABUTIT 620

Modified white hardener for sodium silicates with improved water resistance and high pressure strength

FABUTIT 623

Modified and accelerated hardener for potassium silicates with improved water resistance and high pressure strength

LONGTIME HARDENER / THERMAL HARDENER > 50 C

FABUTIT 206

Hardener for all types of waterglass

FABUTIT 555

Modified hardener for all types of waterglass

3.1. PRODUCT DATA OF OUR HARDENERS

Type of waterglass Lithium Sodium

FABUTIT hardener

Type of hardener

Setting*

FABUTIT 305 FABUTIT 624 FABUTIT 748 FABUTIT 320 FABUTIT 620 FABUTIT 588 FABUTIT 623 FABUTIT 758 FABUTIT 574 FABUTIT 206 FABUTIT 555

standard standard modified modified modified; white powder standard modified standard modified standard modified standard modified modified; white powder standard modified standard modified standard modified

normal accelerated normal normal normal retarded retarded retarded retarded thermal setting thermal setting accelerated accelerated accelerated accelerated accelerated normal normal thermal setting thermal setting

Potassium

FABUTIT 748 FABUTIT 320 FABUTIT 620 FABUTIT 588 FABUTIT 623 FABUTIT 758 FABUTIT 574 FABUTIT 206 FABUTIT 555

* The setting time depends on the concentration, the module and the quantity of the used waterglass and the amount of the FABUTIT hardener accelerated setting : normal setting : retarded setting : within 1 hour within 5 hours within 24 hours

Type of hardener

Bulkdensity (g/l)

P2O5content (%) 80 67 40 52 50 74 40 48 64 60 78

Al2O3content (%) 19 17 24 13 13 24 23 16 31 35 21

pHvalue (10%) 4,0 2,1 6,0 6,0 6,8 3,5 6,0 6,5 2,7 3,5 3,0

Appearance

FABUTIT 206 FABUTIT 305 FABUTIT 320 FABUTIT 555 FABUTIT 574 FABUTIT 588 FABUTIT 620 FABUTIT 623 FABUTIT 624 FABUTIT 748 FABUTIT 758

800 550 550 600 600 800 550 600 700 650 800

fine, white powder fine, white powder fine, grey powder fine, grey powder fine, grey powder fine, white powder fine, white powder fine, grey powder fine, white powder fine, white powder fine, white powder

4. THE BONDING AGENT WATERGLASS

4.1. WATERGLASS

Waterglass is a melted product made of quartz-sand and soda or potassium hydroxide depending on whether sodium or potassium silicate is produced. The production of waterglass is done at a temperature next to 1400 C with a subsequent cooling down . The lumpy glass will then be dissolved in water.

Waterglass gets its name from the property of being soluble in water and thats what clearly distinguishes it from ordinary glass. The solutions are either used directly or dried in a spray drier to form a powder.

The silicate ions in waterglass solutions show different degrees of polymerisation. The solutions are different in concentration, pH-value, viscosity, density and the ratio by weight of SiO2 and Me2O (Me = Na, K or Li). The ratio by weight can be used to calculate the molar ratio, which is also called module.

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The module is calculated as follows :

Sodium silicate:
%SiO 2 %Na 2 O 1,032

Potassium silicate:
%SiO 2 %K 2 O 1,566

The factors in the module formula are calculated on the bases of the molar ratio.

The module indicates the ratio of SiO2 to Me2O. The higher the module , the higher the ratio of SiO2 respectively the lower the ratio of alkali. Therefore types of waterglass may differ because of their module in the following ways:

Classification of waterglass Alkaline waterglass Neutral waterglass (High-silica) Acid waterglass

Module < 2,5 2,5 3,4 > 3,4

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4.2. TYPES OF WATERGLASS

There is a huge variety of waterglass. The products below mentioned are used in the building-, ceramic-and refractory industry. The following silicate types were tested in our laboratory with good results:

Powder / Granular form

Sodium silicates Glassil N Britesil C 20 Lithopix S 2

Module 2,1 2,1 2,1

Supplier Basstech, USA PQ Zschimmer & Schwarz, Lahnstein

Pottasium silicates Kassolv 16

Module

Supplier PQ

Solutions

Sodium silicates Na 40/42 Na 50/52 DS

Module 3,3 2,1

Supplier Woellner, Ludwigshafen Woellner, Ludwigshafen

Potassium silicates K 42 K 5020T

Module 2,9 2,5

Supplier Woellner, Ludwigshafen Woellner, Ludwigshafen

Other producers of waterglass are Van Baerle or Cognis, as well as regional producers in diverse countries.

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4.3. DISSOLUTION SPEED OF WATERGLASS DEPENDING ON THE MOLAR RATIO

4.3.1. Sodium silicate

The average solubility in water in % after 1 minute / 5 minutes

Module 3,2 3,4 2,4 2,6 2,1 2,2

4 C 10 / 12 9 / 27 20 / 65

10 C 12 / 17 27 / 62 57 / 97

20 C 25 / 20 65 / 85 95 / 100

40 C 45 / 45 97 / 100 100 / 100

Solubility decreases with increasing module of the waterglass. 4.3.2. Potassium silicate

The average solubility in water in % after 1 minute / 5 minutes Module 3,0 3,1 grob fein 20 / 50 27 / 85 50 / 85 55 / 97 90 / 97 97 / 100 100 / 100 100 / 100 4 C 10 C 20 C 40 C

Contrary to potassium silicates, sodium silicates as a powder dissolve in water in and exothermic reaction. Temperature increases up to 25 K ( D T), depending on the required quantity and the ambient temperature. The exothermic reaction must be taken into account, as it leads to an acceleration of the system. The main factors which influence the dissolution speed of waterglass are :

- Ambient temperature - Drying method - Specific surface area - Grain size distribution

- Loss on ignition - Waterglass module - Bulk density

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SAMPLE APPLICATIONS
5.1. POWDERED SODIUMSILICATE IN COMBINATION WITH FABUTIT 748

A fast dissolving sodium silicate powder with a module of 2,1 to 2,2 is preferably used for the production of ready mixed mortars and masses. The main hardener used for this purpose is for example FABUTIT 748, which is premixed with fillers in a dry condition. Fillers can be silica sand, silica dust or moulding sand for example. It is absolutely necessary to premix all ingredients including the hardener and the powdered waterglass. This is the only way to soften the fast reaction between the waterglass and the hardener, which , without these fillers, will lead to agglomeration. Having been mixed with tempering water, the mix/ mass seems to be too dry, but after a short mixing time, the mortar will be liquefied. At this stage the sodium silicate is dissolved and the reaction with the hardener starts. The setting time is approximately 90 to 180 min.

Guide formulation:

Fillers Sodium silicate, powder * FABUTIT 748 Water

168 24 8 25

parts by weight parts by weight parts by weight parts by weight

The ratio of water to waterglass should be kept at 1:1. The viscosity of the mix should not be adjusted by adding additional water, this will influence the physical and chemical properties due to the higher porosity (pressure strength, setting time) in a negative way. As fillers especially those materials are suitable, which do not absorb any water and have an almost spherical shape. The modified hardeners improve the strength and the resistance of the masses and require an elevated addition ratio by a factor of 1,5 compared to the standard grade.

* for example Glassil N, Lithopix S 2 or Britesil C 20

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5.2. LIQUID SODIUMSILICATE IN COMBINATION WITH FABUTIT 748

Instead of using a sodium silicate powder, masses and mortars can be formulated with a liquid sodium silicate and FABUTIT-hardeners. For this purpose all dry ingredients are premixed. Then the waterglass is added to the powdered ingredients with a following mix. After a short while this 2 component system is ready to be used.

Guide formulation :

Fillers Sodium silicate, liquid * FABUTIT 748 Water

168 47,5 8 4

parts by weight parts by weight parts by weight parts by weight

The setting time of this mix is above approximately 90 to 180 min. * for example Na 50/52 DS

5.3 LIQUID POTASSIUM SILICATE IN COMBINATION WITH FABUTIT 758

Potassium silicates are used rather than sodium silicates because of their higher acid resistance and the reduced tendency of efflorescence. With its module of 2,9 it is preferably used for acid resistant mortars. A powder type formulation of the mix contains FABUTIT 758 as hardener and fillers are mixed with the liquid waterglass.

Guide formulation :

Fillers FABUTIT 758 Potassium silicate, liquid *

193 9 62

parts by weight parts by weight parts by weight

Such a mix has a pot life of approximately 90 -180 min. * for example K 42

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5.4. GENERAL INFORMATION

Higher temperatures will reduce the setting time, lower temperatures will slow down the reaction. No mix or mortar should be prepared at temperatures below 5 C . It is very important that the mix should be given enough time and should have sufficient moisture to guarantee a complete reaction. A fast drying should be avoided, as it leads to a fast setting time, but also to a slow hardening process which will result in lower strength.

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3. TESTS
6.1. DETERMINATION OF THE COLD PRESSURE STRENGTH OF MIXES AND MORTARS BASED ON WATERGLASS

A mortars strength is characterized by its cold pressure strength. In order to measure this, 4 cylindrical test items (25 mm x 25 mm) are prepared and tested with a hydraulic pressure machine (for exampleTONITROL) after 28 days of drying at ambient temperature.

6.2. DETERMINATION OF THE ACID RESISTANCE OF MIXES AND MORTARS BASED ON WATERGLASS

Masses and mortars based on waterglass are often used in areas, where the material is exposed to acids and chemicals. Therefore the determination of the acid resistance is an important criterion. The test items, which are made and stored as indicated in 6.1., are doused with 70 % sulphuric acid in a beaker and stored for 24 hours at ambient temperature. After 24 hours the test items are taken out the sulphuric acid and cooked out with demineralised water until the washing water is acid free. Afterwards the test items are dried at 110 C until we get a constant weight. This loss in weight is identified in the following formula:

Acid resistance =

m acid m dry m dry

100

Mdry = test item weight before acid resistance test Macid = test item weight after acid resistance test

The loss in weight is an indicator for the acid resistance. The higher the loss in weight, the worse the acid resistance.

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6.3. DETERMINATION OF THE WATER RESISTANCE OF MIXES AND MORTARS BASED ON WATERGLASS

The resistance of masses and mortars based on waterglass against condensate respectively water is of great importance in many applications. Therefore water resistance is another important criterion.

The test items, which are made and stored as indicated in 6.1., are doused with water in a beaker and stored for 24 hours at ambient temperature. After 24 hours the test items are taken out of the water and dried at 110 C unt il we get a constant weight. The loss in weight is an indicator for the water resistance and is calculated with following formula.

Water resistance =

m dry m water m dry

100

Mdry = test item weight before water resistance test MWaterr = test item weight after water resistance test

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Chemische Fabrik Budenheim KG Rheinstrasse 27 55257 Budenheim Germany Phone ++49.+6139.89.0 Fax ++49.+6139.89.264 info@budenheim-cfb.com www.budenheim.com

Any information contained herein and any advice given by CFB is made to the best of our ability on the basis of current industrial practice and our ownknowledge and experience. Any responsibility for damages resulting from the use of or reliance upon such information or products such information refers to is limited pursuant to our Conditions of Sale and Delivery. Neither our advice nor any information contained herein shall cause the purchaser or any other person or entity using our products to refrain from testing our products and verifying any suggestions contained in our information or reviewing conflicting patent and proprietary rights; and we expressly request and invite the customer or such other user of our products to perform such tests or have such tests performed prior to any commercial use or application of our products for the specific use and application intended.