DE60024483T2 - MULTIPHASIC CALCIUM SILICATE HYDRATES, PROCESS FOR PREPARING THE SAME AND IMPROVED PAPER AND PIGMENT PRODUCTS CONTAINING THEM - Google Patents

Abstract

A method for the hydrothermal preparation of calcium silicate hydrates. Multi-phase calcium silicate hydrates, having unique physical and chemical properties, are prepared by hydrothermal reaction of specified ratios of CaO and SiO2, normally starting from slurries of slaked lime and from fluxed calcined diatomaceous earth, each of which is at about the atmospheric boiling point before being mixed and charged to a reactor, and pressurized. The hydrothermal reaction is carried out while maintaining the initial dilution for a preselected reaction time at a preselected reaction temperature. The calcium silicate hydrates produced have high water absorption and light scattering power, and have optical and physical properties making them highly desirable as a filler substitute in papermaking.

Description

FIELD

These The invention relates to the preparation of novel crystalline Calcium silicate hydrate ("CSH") structures and on pigment products and novel paper products made therewith.

BACKGROUND

The Paper industry currently uses many different types of fillers, to replace pulp fibers and the desired functional and performance characteristics to achieve different papers and paper products. For a long time, e.g. Alumina is used as filler or fiber substitute. It was important that the use of clay was also an improvement the print quality causes. A disadvantage of clay, however, is that he has one relatively low whiteness Has. Furthermore leads the Use of clay in papermaking at a reduced rate Tensile strength and reduced thickness and stiffness of the leaves.

The Paper industry went over to using calcined clay to the whiteness and the opacity of the paper. For economic reasons However, the use of calcined clay only limited possible since he is relatively expensive. Furthermore For example, calcined clay is high in its physical nature abrasive.

Titanium dioxide (TiO ₂ ) is another example of a filler that is commonly used in papermaking. Mostly titanium dioxide is used to improve the opacity of the paper, in some cases also to increase its whiteness. However, the use of titanium dioxide is limited, since it is extremely expensive. Unfortunately, it is also the most abrasive of all pigments on the market today. This plays an important role, because highly abrasive pigments have a detrimental effect in the paper industry in that they lead to the wear of critical parts of the paper machines, eg the forming wires, the plates of printing presses and similar components. The ongoing repair and maintenance costs entail high life cycle costs.

When calcined clay was first introduced, it was offered as an extender for titanium dioxide. It was actually able to stretch TiO ₂ , but it is still abrasive and more expensive than standard clay or commercially available pulp fibers.

In younger Time, especially since the mid-1980s, was ground calcium carbonate (GCC) used as a cheap alkaline filler. GCC improved although the whiteness of the paper, but also has the disadvantage that it is abrasive.

Also reduced the use of GCC's tensile strength, thickness and rigidity the paper sheets. As a result, paper containing GCC is usually relatively soft.

one the most common used alkaline fillers for paper is finally likes this Calcium carbonate (PCC). PCC is currently one of the best compromise solutions, if you have a filler with high whiteness wants to use at an economically reasonable price.

However, a significant disadvantage of using PCC in paper is that PCC has a lower light scattering capability than TiO ₂ or calcined clay. In addition, it often reduces the thickness and stiffness of the sheets.

• a) geringere Kosten als sie für TiO₂ anfallen;
• b) bessere optische Eigenschaften als calcinierter Ton;
• c) bessere optische Eigenschaften als GCC;
• d) bessere optische Eigenschaften als PCC;
• e) minimaler Verlust an Zugfestigkeit bei erhöhtem Füllstoffeinsatz;
• f) mindestens eine geringfügige Verbesserung der Festigkeitseigenschaften wie etwa der Steifigkeit der Blätter.

Thus, there is still room for improvement in the paper industry and the desire for a multifunctional pigment that combines two or more of the following attributes:

• a) lower costs than for TiO ₂ ;
• b) better optical properties than calcined clay;
• c) better optical properties than GCC;
• d) better optical properties than PCC;
• e) minimal loss of tensile strength with increased filler usage;
• f) at least a slight improvement in the strength properties such as the stiffness of the leaves.

If a paper filler additionally to the above criteria also the porosity of the paper improve (i.e. the bows would make it more closed) and yet could provide a higher sheet density would be such Material as filler much sought after. So far, there was no paper filler in the market with these attributes. That's why the development and commercial availability of such a filler is highly desirable.

Of the Today's demand for printing papers, especially the rapidly increasing Need for papers for Inkjet printer, requires the provision of high performance paper. The efficiency such papers would through the availability of a pigment increases, the above an excellent water and oil absorption capacity features, so that the paper can absorb the ink quickly and spread out or prevent bleeding. In addition, the surface would dry the ink supports.

Some the essential requirements for an ideal pigment for papermaking can as summarized in Tables 1, 2 and 3 below become.

Table 1:

The paper industry is currently using various combinations of available fillers to optimize the properties desired in certain papermaking applications. Because the However, currently available fillers at least slightly reduce the strength of the paper, the industry resorts to additives that increase strength such as starch and / or polymers to achieve the desired strength properties, although fillers are used. Unfortunately, due to the different particle loading characteristics of the various pigments, the addition of multiple pigments and additives in papermaking often results in an extremely complicated chemical system that can be quite sensitive and difficult to control.

Summarized It can be said that continues to be a significant and not yet fulfilled There is a need for a high quality, low cost filler that uses can be used to simultaneously achieve the desired optical properties and leaf thicknesses to achieve paper products. In addition, a method is still missing to the reliable Preparation of such a pigment that the desirable optical properties and that compared to the use of titanium dioxide or other pigments currently used in papermaking cost benefits.

OBJECT, ADVANTAGES AND NEW FEATURES OF THE INVENTION

Accordingly An important goal of my invention is a process to produce unique calcium silicate hydrate ("CSH") products that are crystalline Structures with the desired Whiteness, the desired opacity and other desired provide optical properties.

One Another and related goal is the provision of a economically usable substitute for the current paper fillers like titanium dioxide.

One the associated important goal is to provide a method for making novel paper products using my unique calcium silicate hydrate products.

One another important goal is to provide a new calcium silicate hydrate product, that as properties u.a. a low bulk density, a good chemical stability (especially in watery Solutions) and a high adsorption capacity having.

These and other advantages and novel features of my multiphase Calcium silicate hydrates, their method of preparation and the improved Pigments and paper products made with it by the overall consideration and evaluation in the following detailed Description and attached Tables and graphs easier to understand and assessable.

SUMMARY

I I have now discovered the process conditions necessary for reliable production of unique calcium silicate hydrate products with particularly advantageous Properties for the use as a filler in papermaking are required. The products are made, under hydrothermal conditions a slurry of burnt lime and a slurry of fluxed calcined kieselguhr (or another suitable siliceous Material) are reacted. Preferably, a fine slurry of both the lime and the fluxed silica.

For one of my CSH products, lime slurry is made using about 1.54 lb (pounds) of suspended solids per gallon of lime mud. The silica slurry is prepared using 1.55 lbs of suspended solids per gallon of water. The deletion of the lime slurry raises the temperature of the slurry almost to the boiling point; only then is the mass added to the fluxed silica. The slurry of fluxed calcined kieselguhr is also heated to a temperature near the boiling point before it is mixed with the lime slurry. As both slurries approach atmospheric boiling point conditions, they are mixed together and stirred under pressure in an autoclave or similar reaction vessel. The reaction slurry is heated to a temperature between 245 ° C and 260 ° C and the reaction is continued for about two hours. In the starting materials, a CaO / SiO ₂ ratio of about 1.35 (+/- about 0.10) moles of CaO to 1 mole of SiO _{2 is} maintained. After completion of the reaction, the product is cooled before the pressure is released and the product crystals are removed.

In general, the product of the reaction described above is a multi-phase mixture (ie, there are two different forms or phases in the product), predominantly foshagite and a minor amount of xonolite. What is important is that small, heuschaufenartige particles with complex mehrphasi crystalline optical fibers are formed, which can be used in the papermaking advantageous for coating and for wet-end fillers. However, the multiphase crystalline optical fibers prepared hydrothermally are significantly improved over the previously prepared hydrothermal calcium silicate hydrates known to me, at least in view of their physical properties, optical properties, and usability as a papermaking filler. In addition, my unique CSH products can be used for a variety of purposes, such as fillers for high-quality papers, plain consumer papers, newsprint, paper coatings, paints, rubber compounds, and other structural materials.

It can be seen that my hydrothermal process for making my unique multiphase calcium silicate hydrates ("CSHs") including my novel multiphase blend of foshagite and xonolite (CaO ₄ (SiO ₃ ) (OH) ₂ and C ₆ Si ₆ O ₁₇ (OH), respectively). ₂ ) yields a unique blend of calcium silicate hydrates that has a unique and characteristic X-ray diffraction pattern.

• (1) Ein mehrphasiges Calciumsilicathydrat mit einer primären Foshagit-Phase und einer sekundären Xonolit-Phase. Ich bezeichne dieses Produkt als Calciumsilicathydrat der Marke „TiSil".
• (2) Ein mehrphasiger Calciumsilicathydrat-Komplex mit einer primären Riversideit-Phasenfraktion und einer geringeren Xonolit-Phasenfraktion. Ich bezeichne dieses Produkt als Calciumsilicathydrat der Marke „StiSil".

The variables that affect the chemical composition of my CSH product and the primary and secondary structure of the CSH particles and their characteristic properties can be influenced, inter alia, by (a) the CaO / SiO ₂ molar ratio, (b) the concentration the CaO and SiO ₂ in the reaction sludge, (c) the reaction temperature and (d) the reaction time. By changing the variables mentioned, I was able to develop two novel pigment products. These two products can generally be described as follows:

• (1) A multi-phase calcium silicate hydrate having a primary foshagite phase and a secondary xonolite phase. I refer to this product as "TiSil" brand calcium silicate hydrate.
• (2) A multiphase calcium silicate hydrate complex having a primary Riversideite phase fraction and a lower Xonolite phase fraction. I refer to this product as calcium silicate hydrate brand "StiSil".

The first product is formed at a high CaO / SiO ₂ molar ratio (ratio of CaO to SiO ₂ about 1: 1 to about 1.7: 1), high temperature (200 ° C-300 ° C), low final concentration of Slurry (~0.4-0.6 lb solids per gallon of slurry) and a reaction time of about 2 hours. It has the characteristic X-ray diffraction pattern that is found in 1 is shown. The scanning electron micrographs (SEMs) of this product are in the 2 and 3 shown. As the REMs indicate, this product consists of interconnected primary fibrous particles that form a secondary three-dimensional "haystack structure." The physicochemical characteristics of this product are unique, such as extremely high water absorption When used as a filler, it can simultaneously improve the optical properties as well as the thickness, volume, smoothness and porosity of the paper.

The second product is formed by mixing lime and silica at a low molar ratio (about 0.85: 1 of CaO to SiO ₂ ), low reaction temperature (180 ° C to 190 ° C), high final slurry concentration (~0.7-1 , 0 lb solids per gallon of slurry) and reacted with a reaction time of about 2 hours. This calcium silicate is significantly different from the first product mentioned above. His unique X-ray diffraction pattern is in 4 shown. The scanning electron micrographs (SEMs) for this product are in the 5 and 6 shown. As the SEMs show, this product consists of some fibrous structures that grow randomly and almost continuously to give an irregular spherical structure. This product is uniquely suited for producing extremely high sheet stiffness when used as a paper filler.

• • eine einzigartige kristallo-chemische Zusammensetzung
• • ein mehrphasiges Kristallsystem
• • eine primäre und eine sekundäre faserige Teilchenstruktur
• • ein hohes Wasserabsorptionsvermögen (im Bereich von –300%–1000%).

In summary, these hydrothermally produced calcium silicate hydrate products have the following unique characteristics:

• • a unique crystallo-chemical composition
• • a multiphase crystal system
• • a primary and a secondary fibrous particle structure
• • a high water absorption capacity (in the range of -300% -1000%).

Because of their unique properties and their physical structure, these unique CSH products are able to give paper products a combination of beneficial properties in a manner previously unknown in paper fillers. For example, using these products in paper can increase paper volume and Gurley porosity simultaneously. In addition, while these products are made up of large particles, the light scatters PCC, GCC, clay or even calcine better sound.

DETAILED DESCRIPTION

To make my unique calcium silicate hydrate (CSH) products, a calcium source must first be provided. This is normally done by making a slurry of calcium containing material, usually lime. However, different calcium sources can be used. Some examples are CaCO ₃ , CaCl ₂ and hydrated lime. I found the use of silica with a size of less than ½ inch advantageous. First, the CaO was quenched in water. The amount and the rate of addition of the lime were set and maintained to obtain a desired concentration of the lime slurry. Since the deletion of lime is an exothermic process, both the rate of addition of the lime and the amount of water used had to be regulated. When extinguishing, a temperature near the boiling point was determined as the optimum temperature, ie about 100 ° C (212 ° F), so that as fine as possible lime particles. After completion of the quenching, the lime slurry was passed through a 200 mesh sieve to remove foreign matter and oversize particles. The sieved and quenched lime slurry was tested for available lime (as CaO) and then transferred to an autoclave. The chemistry of the quenching process can be represented as follows:

The solubility of calcium hydroxide sludge is inversely proportional to the temperature, as in 7 shown.

Next, a slurry of silicon-containing material must be made (ie, a SiO ₂ slurry). In this case, various silicon-containing materials such as quartz, water glass, clay, pure silica, natural silica (sand), diatomaceous earth, fluxed calcined diatomaceous earth or any combination of these materials can be used as Ausgangsma material. I prefer to use ultrafine fluxed calcined diatomaceous earth. From this feed, a slurry of -1.55 pounds of solids per gallon of water was made. The sludge was then preheated to almost the boiling point, ie to almost 100 ° C.

Importantly, the solubility of silica (unlike that of Ca (OH) ₂ ) is directly proportional to temperature, as in 8th can be seen. Quartz (line A in 8th ) is, for example, only slightly soluble up to 100 ° C. Between 100 ° C and 130 ° C quartz begins to dissolve and reaches its maximum solubility of approx. 0.7% at a temperature of approx. 270 ° C.

The dissolution of silica can be represented as follows: (SiO ₂ ) _n + 2n (H ₂ O) → n Si (OH) ₄ 3)

The solubility of silica may be due to an increase in pH and / or the Use of various additives (sodium hydroxide) can be increased. The degree of solubility of the silica is also dependent from the particle size. Therefore I prefer to use ultrafine fluxed calcined kieselguhr, about the solubility of the silica.

Next, the silicon-containing slurry was mixed with the lime slurry in an autoclave to achieve a hydrothermal reaction of the two muds. Importantly, the amount of CaO in the lime slurry and the amount of SiO ₂ in the slurry of the fluxed calcined kieselguhr were set in advance to achieve a certain CaO / SiO ₂ molar ratio. In addition, the concentration of the two slurries (CaO and SiO ₂ ) was chosen such that the final concentration of the reaction mixture in the autoclave was 0.2 lb solids per gallon of sludge to about 1.0 lb solids per Gallon of mud went back.

• 1) Aufheizen der Aufschlämmung auf die gewünschte Temperatur (z.B. 180°C bis 300°C)
• 2) Ablauf der Reaktion bei dieser Temperatur über eine festgelegte Zeit (z.B. 60 Min. bis 240 Min.)
• 3) Stoppen der Reaktion und Abkühlen

The hydrothermal reaction itself was carried out in a pressure vessel in three main steps:

• 1) heating the slurry to the desired temperature (eg 180 ° C to 300 ° C)
• 2) Procedure of the reaction at this temperature for a fixed time (eg 60 min. To 240 min.)
• 3) Stop the reaction and cool

In my lab, the reaction autoclave was cooled by passing extinguishing water through an internal cooling coil or using an external jacket cooling system. I prefer a cooling process of about 25 to 30 minutes to reduce the temperature from about 230 ° C to about 80 ° C, as in 9 shown.

The mentioned above Process steps are very important as I have the reverse solubilities of lime and silica depending on the temperature and used the time to prepare the desired reaction mixture and so to the desired multiphase calcium silicate hydrate product to arrive.

Without restricting my invention to any particular theory, I can postulate the following reaction during the hydrothermal reaction between calcium-containing and silicon-containing material. At the beginning, very few Ca ++ ions are available during the heating process. At a temperature above 100 ° C, the silica begins to pass into a gel state. At a temperature above 130 ° C, the silica ions become available for the reaction. As the temperature approaches 180 ° C, the calcium ion Ca ++ reacts with the Si + ion to form a metal silicate. The reaction can be expressed as follows: x [Ca ⁺⁺ + 2OH ^- ] + y [Si (OH) ₄ ] → Cao _x (SiO ₂ ) _y + (x + y) H ₂ O 4)

Where:
x = 1 to 6
y = 1 to 6

The solid Ca (OH) ₂ particles react with SiO ₂ in the gel phase to form a calcium silicate hydroxide whose crystallo-chemical structure can be expressed as Ca ₆ Si ₆ O ₁₇ (OH) ₂ (xonotlite). As the temperature is further increased from 180 ° C to 250 ° C, the calcium silicate hybrid product condenses with the remaining Ca (OH) ₂ particles to form another calcium silicate hydroxide, this time with a characteristic X-ray diffraction pattern and the crystallo-chemical Formula CaO ₄ (SiO ₃ ) ₃ (OH) ₂ (Foshagit).

• 1) Löschtemperatur
• 2) CaO/SiO₂-Molverhältnis
• 3) Konzentration der Aufschlämmung
• 4) Reaktionstemperatur
• 5) Reaktionszeit bei dieser Temperatur

I've developed my hydrothermal reaction process to make more than a unique calcium silicate hydrate. In this context, it is important to note that the following variables are critical to the production of a desired end product:

• 1) extinguishing temperature
• 2) CaO / SiO ₂ molar ratio
• 3) Concentration of the slurry
• 4) reaction temperature
• 5) reaction time at this temperature

By change This variable can be used to make a product containing calcium silicate hydroxide in contains different phases. To these phases can belong:

Although it does not usually play an important role, it should be noted that the CSH co The composition of my final product may also contain small amounts of calcite aragonite, which may be the result of side reactions.

The first and most important product of my process is a multiphase CSH composition with matter in different phases in the form of CaO ₄ (SiO ₃ ) ₃ (OH) ₂ (foshagite) and Ca ₆ Si ₆ O ₁₇ (OH) ₂ (xonotlite). In 1 a unique X-ray diffraction pattern (RBM) is shown for this product. The crystallo-chemical formula of the mixture underlying this RBM and the characteristic d-spacings are given below:

The scanning electron micrographs (SEMs) of this first product are in the 2 and 3 played. As in 2 and 3 It is important to note that the product consists of primary and secondary particles.

The primary particles have a diameter between 0.1 and 0.2 microns and a length between 1.0 and 4.0 microns. 3 also shows that the primary particle has two phases. The rod-like or ribbon-like structure is characteristic of xonotlite (Ca ₆ Si ₆ O ₁₇ (OH ₂ )), while the predominant structures are thin and fibrous, which is characteristic of foshagite (Ca ₄ (SiO ₃ ) ₃ (OH) ₂ ) , The diameter of the Foshagit crystals is between 0.1 and 0.3 microns and their length is between 2.0 and 5.0 microns.

The REM in 3 lets recognize a secondary three-dimensional structure. This three-dimensional structure is probably due to the interlocking of the fibrous material and the continuous growth of the "gel-like" material at the point of intersection of the individual particles, which may also be the reason why the secondary structure is quite stable Secondary structure generally resists the shearing forces that occur when the material is removed from the pressure vessels after the end of the reaction, as well as the shear forces that occur in papermaking, as evidenced by the secondary structure's "bulk density" during some the finishing processes such as calendering in papermaking. The particle size of the secondary structure measured with particle measuring devices such as the Malvern Mastersizer ranges between 10-40 microns.

The Calcium silicate-hydroxide mixture of my invention also has a very high whiteness. Below is a comparison with other pigments:

Various Pigments and their typical published Whiteness values:

A the most significant properties of the composition, the The result of my process is the ability of this multiphase Calcium silicates, large To absorb quantities of water. These calcium silicates can be any Amount between 350% and 1000% of their own weight adsorb. By this high water absorbency is my pigment best suitable for the penetration of ink through writing and printing papers, Prevent newsprint and other papers.

Example 1: Preparation of multiphase silicate hydrates (5XPC 12)

First, 135.09 grams of 1/2 "rotary kiln silica (Mississippi Lime Co.) was accurately weighed and quenched in 410 milliliters of deionized water. The quenching reaction is exothermic and allowed the temperature of the slurry to rise almost to the boiling point. When the temperature of the slurry was near the boiling point and before much of the water had evaporated, an additional 1190 milliliters of water was added to dilute and cool the slurry. The slurry was then agitated for 30 minutes to ensure complete extinguishment before being passed through a 140 mesh screen. The slurry was then placed in a 5 liter autoclave and tested for lime availability according to ASTM method C25. The autoclave was equipped with an external heating element housed in an insulated jacket. The autoclave was also equipped with a variable speed magnetic drive for stirring the slurry during the reaction. Approximately 109.6 grams of ultrafine fluxed calcined diatomaceous earth were weighed and added to 750 ml of hot water (concentration: 1.22 lb / gallon). The silica slurry was heated to near boiling point for about 10 minutes and then added to the screened and tested lime slurry. The exact amount of the silica slurry added to the lime slurry was determined from the lime availability, so that a molar ratio of 1.35 moles of CaO / SiO ₂ could be obtained. The total volume of the slurry was also adjusted to a final concentration of 0.425 lb / gallon. Subsequently, the high-pressure vessel was closed, sealed and connected to an automated heating-cooling system (RX 330). The content of the autoclave was constantly moved by means of the above-mentioned magnetically driven motor.

• 1) Röntgenbeugungsanalyse
• 2) Rasterelektronenmikroskopische Aufnahmen (REM)
• 3) Weißgrad
• 4) Prozentuale Wasserabsorption
• 5) Luftdurchlässigkeit (Blaine-Methode)
• 6) pH-Wert

The high pressure reactor was heated by an external jacket heater. The autoclave was moved at a constant speed of 338 rpm. The reactor was heated for about 100 minutes to reach the target temperature of 245 ° C (473 ° F). The temperature was maintained at 245 ° C for two hours after reaching the target temperature using the temperature control. At the end of the reaction, the "quench water" was passed through the cooling coil inside the autoclave, and this cooling process was continued until the internal temperature in the vessel reached about 80 ° C (about 30 minutes), and then the vessel was opened Part of the slurry resulting from the process was dried in a 105 ° C. oven for 12 hours During the drying process, hard slugs emerged from the sludge which had to be crushed using a mortar and pestle. The now pulverized, dry product was brushed through a 140 mesh screen to ensure product uniformity for the tests The pigment in this example was designated 5XPC 12. The following tests were performed on the dry powder:

• 1) X-ray diffraction analysis
• 2) Scanning electron micrographs (SEM)
• 3) whiteness
• 4) Percent water absorption
• 5) Air permeability (Blaine method)
• 6) pH

in the Air permeability test two values were determined. The first is the weight of the powder in grams, that needed will be to fill the capsule. It indicates the "bulk density" of the powder. The second value is the time in seconds that a controlled one Amount of air to pass the compressed powder in the capsule needed. It provides an approximate Measurement of the "structure" of the particle.

The Process conditions are described in Table 1a, the pigment properties in Table 1b.

Table 1a:

Table 1b:

The X-ray diffraction pattern of this novel multiphase calcium silicate hydrate is in 1 shown. This product (called 5XPC 12) showed a unique X-ray pattern. The sample showed that the powder has a larger phase and a smaller phase. The summary of the characteristic "peaks" is shown in Table 1c.

The large peaks for phase I were found to be the presence of calcium silicate hydroxide foshagite (Ca ₄ (SiO ₃ ) ₃ (OH) ₂ ) with large peaks at d (Å) = 2.97, d (Å) = 2.31 and a small peak at d (Å) = 5.05. For phase II, the X - ray diffraction pattern showed the presence of calcium silicate hydrate - xonotlite - (Ca ₆ Si ₆ O ₁₇ (OH) ₂ ) with large peaks at d (Å) = 3.107, d (Å) = 1.75, and a small peak d (Å) = 3.66. I have thus gained from a single reaction a novel combination of Foshagit and Xonotlite.

Table 1c:

The SEM images with 10,000x and 2000x magnification are in the 2 respectively. 3 shown. The high magnification SEM clearly shows the fibrous structure of Foshagit and a small proportion of rod-like or ribbon-like tubular structures of xonotlite. The diameter of the Foshagit "fibers" is between 0.1 and 0.2 microns, their length is between 1 and 3 microns, and the xonotlite particles have diameters ranging between 0.1 and 0.3 microns and a length in the range of 1 to 3 microns.

The lower magnification SEM shows the three-dimensional structure of the secondary particles of calcium silicate hydrates. The structure appears to have been formed by the interlocking of the "fibrous" primary crystals and, in part, by inter-fiber bonding through silica hydrogel formed in the first stages of the hydrothermal reaction, which are the two main reasons that the secondary particles are right Stable and largely retaining their 3D structure when exposed to the shear forces of the process, these particles also appear to withstand the pressure experienced in calendering or final process steps in papermaking, the average size of the secondary particles being, as noted From 10 to 40 microns, to evaluate this pigment when used in paper, handsheets were prepared for evaluation and the handsheets were made using the product pattern 5XPC 12 to determine the properties of the pigment in papermaking the production of a standard pulp of 75% hardwood and 25% softwood. Both pulp sources were separately ground in a Valley mill to a specific Canadian standard freeness of 450 ± 10 according to the TAPPI test methods T-200 and T-227 ground. The handsheets were molded from the prepared material on a British 6 "laboratory sheet in accordance with TAPPI T-205 test method. The following deviations from the standard method were present. Since the goal in preparing these handsheets was to test the filler performance, filler was added to the handsheets in varying amounts (usually 15%, 20% and 25%). To achieve comparability between the different amounts, a constant basis weight was produced by reducing the fiber content. That is, a sheet of 25% filler contained only 75% of the fiber material contained in a sheet without filler. Another departure from the standard test method was the addition of a retention aid. A retention aid (Percol 175) was added to hold the filler in the sheet until the sheet was completely dried. All other components in making the handsheets corresponded to the TAPPI T-205 test method.

The laboratory sheets with one exception according to the TAPPI test method T-220 tested. Instead of a 15mm sample was used to test the tensile strength used a 25.4 mm sample and calculating the tensile index was adjusted accordingly. The handsheets were tested according to the TAPPI test method T-211 ashed.

• 1. Opazität
• 2. Streukoeffizient der Blätter
• 3. Streukoeffizient des Füllstoffs
• 4. Weißgrad
• 5. Volumen (Verhältnis Basisgewicht/Dicke)
• 6. Steifigkeit
• 7. Porosität
• 8. Glätte
• 9. Zugfestigkeitsindex

The handsheets were tested for the following properties:

• 1. opacity
• 2. Scattering coefficient of the leaves
• 3. Scattering coefficient of the filler
• 4. Whiteness
• 5. Volume (ratio basis weight / thickness)
• 6. stiffness
• 7. Porosity
• 8. Smoothness
• 9. Tensile index

It became a standard alkaline filler, likes this Calcium carbonate (PCC) (SMI Albacar HO), used as reference material, to determine the product performance. The results from the evaluation the lab sheets are shown in Tables 1d and 1e.

Table 1d:

Table 1e:

Table 1f:

Table 1g:

Example 2 - (pigment pattern 5XPC - 27)

This novel multiphase calcium silicate hydrate was prepared by a hydrothermal reaction of lime and silica. The CaO / SiO ₂ mole ratio used for this new product was 0.85, the final concentration of the slurry was -0.8 lb / gallon, the reaction temperature 190 ° C and the reaction time 2.5 hours. A summary of these conditions is given in Table 2a.

Using a new combination of reaction conditions created a completely new product. First, the CaO / SiO ₂ molar ratio was adjusted to 0.85, the reaction temperature was 190 ° C, the slurry concentration was increased to 0.75 lb / gal, and the reaction time was extended to 2.5 hours. The product used in this example was designated 5XPC 27. A summary of the reaction conditions is given in Table 2a.

Table 2a:

The calcium silicate hydrate resulting from the process was tested for whiteness, water absorption, air permeability and Blaine's density, and the pH of the pigment. In addition, an X-ray diffraction analysis and an analysis of the scanning electron micrographs of this product were carried out. The pigment properties are in 2 B played. The pigment was evaluated for performance in paper use by incorporating it into handsheets as in Example 1. The results of the laboratory sheet tests are shown in Tables 2d and 2e. The x-ray diffraction pattern is in 4 shown. The SEM images with 10,000 times and 2000 times magnification are in the 5 respectively. 6 shown.

The calcium silicate hydrate formed under these conditions had one much lower whiteness and water absorption value as the CSH brand TiSil, which is exemplified 1 has been described. It led but to a much higher level Leaf volume and a higher Journal permeability. The Pigment properties of my novel pigment 5XPC 27 are in Table 2b set forth. It seems like this product leads to one much higher Leaf volume. Furthermore was the leaf permeability higher with this new product as in the foshagite-xonotlite complex as described in Example 1 has been.

Table 2b:

By reducing the molar ratio of CaO / SiO ₂ to ~ 0.85 and lowering the reaction temperature to 190 ° C, I discovered another unique and useful multiphase calcium silicate hydrate material having a characteristic and unique X-ray diffraction pattern. The X-ray diffraction analysis shows that this product is a mixture of Riversideite [Ca ₅ Si ₆ O ₁₆ (OH) ₂ ] and Xonotlite (Ca ₆ Si ₆ O 17 (OH) ₂ ] The X-ray diffraction pattern is in 4 shown. The pattern shows that the powder has a large and a smaller phase. The peak summary is shown in Table 2c.

Table 2c:

The large peaks for phase I were found to be the presence of calcium silicate hydrate - Riversideite - (Ca ₅ Si ₆ O ₁₆ (OH) ₂ ) with large peaks at d (Å) = 3.055, d (Å) = 3.58 and a small peak at d (Å) = 2.80. For phase II, the pattern indicated the presence of calcium silicate hydroxide xonotlite (Ca ₆ Si ₆ O ₁₇ (OH) ₂ ) with large peaks at d (Å) = 3.056, d (Å) = 4.09, and a small peak d (Å) = 2.50. The pigment also contained trace amounts of calcite (CaCO ₃ ). The other part of the slurry was tested for the performance of the pigment as a filler in paper. The paper was made into handsheets and tested by the methods described in Example 1.

The SEM images with 10,000 times and 2000 times magnification are in the 5 and 6 shown. As can be seen in the photo with 10,000x magnification, the product looks different than in the previous example. The calcium silicate hydrate mixture has a fibrous and non-fibrous composition which may be linked by an amorphous portion of silica hydrogel formed in the first phase of the hydrothermal reaction.

The 2000x magnification shows the formation of an irregular spherical particle, that by the fibrous interweaving of a series of fibrous ones primary crystals originated. The particle size is in the range of 10-30 Mikron and the crystals seem to have grown arbitrarily.

This multiphase (mainly Riversideite and Xonotlite) calcium silicate hydrate showed a lower whiteness than in example 1. More significant, however, is that this material also has a much lower water absorption (about 360% -400%).

Around the efficiency in paper, laboratory sheets were formed using this pigment and then tested as in Example 1. The results of the performance in paper are shown in Tables 2d-g.

This Product showed a significantly higher stiffness compared to pure pulp and a much higher one Leaf volume. Unlike the pigment in Example 1 (in Foshagit the main component was) led this second pigment combination (in the Riversideite and Xonotlite contained) to a much more open sheet, such as the low Gurley Porositätszahlen demonstrate. The values for the optical properties such as whiteness, opacity and scattering coefficient of the leaf went back.

in the Compared to an alkaline filler how felled Calcium carbonate are in this second pigment (which predominantly Riversideit and Xonotlite contains) the leaf stiffness and the leaf volume much higher. The optical properties (opacity, Brightness etc.) of the handsheets but were less good. The less good optical properties This new multiphase product was clearly on the big particles and the irregular sphere structure, which can be recognized in the SEM images, due.

Table 2d:

Table 2e:

Table 2f:

Table 2g:

These multiphase calcium silicate hydrate composition was thus very useful for Improvement of leaf stiffness and leaf volume. she was Furthermore Ideal for "opening" the sheet (lowering Gurley porosity) for better "breathing". Because of his excellent rigidity I call this product "CSH" of the brand StiSil.

Example 3: Change the reaction temperature (XPC 119)

First, 39.9 grams of siliceous lime were accurately weighed and slowly added to 1.2 liters of water in a beaker with constant stirring. The amount of lime and water and the rate of addition of the lime were controlled to prevent the slurry from starting to boil due to the exothermic nature of the lime slaking reaction. The quenched lime of Ca (OH) ₂ was sieved with a 200 mesh sieve. The remaining material was discarded. The filtered Ca (OH) ₂ slurry was tested by acid titration to determine the exact amount of lime available. The slaked lime was then placed in a 2 liter autoclave. Subsequently, 31.06 grams of ultrafine calcined diatomaceous earth was added to 200 ml of water to prepare a slurry having a concentration of 0.1553 g / liter. This slurry was also heated with constant stirring and brought to almost the boiling point (near 100 ° C). Next, the silica was added to the slaked lime hot slush autoclave. The total solids concentration of the CaO + SiO ₂ slurry in the autoclave at this time was ~ 0.5 lb / gallon. The molar ratio of lime and silica was 1.67 CaO / SiO ₂ . The high pressure reactor was sealed and then heated by an external electric jacket heater.

The autoclave was simultaneously moved by a magnetically driven motor at a constant speed of 600 rpm. The autoclave was heated until a pre-set temperature of 220 ° C was reached. From this point on, the reaction conditions were kept constant by a system controller, RX-32. The CaO + SiO ₂ slurry reacted at a temperature of 220 ° C over a period of 120 minutes. At the end of this period, the "quench water" was passed through a cooling system inside the autoclave, steam condensed in the pressure vessel and the temperature dropped rapidly, and cooling water continued to be supplied until the vessel reached a temperature of about 80 ° C.

• – Zeit bis zum Erreichen der Temperatur ~100 Min.
• – Zeit bei erreichter Temperatur ~120 Min.
• – Zeit für das Abkühlen ~25 Min.

The silicate slurry was placed in a beaker. The following describes the entire heating / cooling cycle (s. 5 ):

• - Time to reach the temperature ~ 100 min.
• - Time at reached temperature ~ 120 min.
• - Cooling time ~ 25 min.

• 1) Röntgenbeugungsanalyse
• 2) Rasterelektronenmikroskop (REM)
• 3) Weißgrad
• 4) Wasserabsorption
• 5) Luftdurchlässigkeit nach Blaine (ASTM/ASTM C204-78a)
• • Probengewicht (g) – Anzeige der Schüttdichte
• • Zeit (in Sek.), die eine bestimmte Menge Luft braucht, um das Probenvolumen zu passieren – Anzeige der Teilchenpackung oder -struktur

Part of the slurry was tested for the following properties:

• 1) X-ray diffraction analysis
• 2) Scanning Electron Microscope (SEM)
• 3) whiteness
• 4) water absorption
• 5) Blaine air permeability (ASTM / ASTM C204-78a)
• • Sample weight (g) - Bulk density indication
• • Time (in seconds) that takes a certain amount of air to pass through the sample volume - Displays the particle packing or structure

The Reaction conditions and pigment properties are shown in the tables 3a and 3b reproduced.

Example 4: Change the reaction temperature (XPC 107)

In In this example all reaction conditions and parameters were identical with example 3, except that the reaction temperature was increased from 220 ° C to 233 ° C. The one from the process resulting calcium silicate hydrate complex was then determined using the tested as described above. The resulting Reaction conditions and pigment properties are shown in the tables 3a and 3b reproduced.

Example 5: Change the reaction temperature (XPC 124)

In This example has all the reaction conditions and parameters constant as in Example 3 except the reaction temperature. The reaction temperature was raised from 233 ° C to 243 ° C. The one resulting from the process Calcium silicate hydrate complex was as in the previous examples tested. The reaction conditions and pigment properties are in Tables 3a and 3b, respectively.

Table 3a:

Table 3b:

It it should be noted that at the average reaction temperature of 233 ° C that Material with the highest whiteness was achieved.

Example 6: Change of the CaO / SiO 2 molar ratio (XPC 130)

In this example, all reaction parameters were kept constant as in Example 4 except for the CaO / SiO ₂ molar ratio. The CaO / SiO ₂ molar ratio was changed to be 1.4.

69.0 g of SiO ₂ and 78.0 g of CaO were mixed, resulting in a CaO / SiO ₂ molar ratio of 1.4. The two slurries, CaO and SiO ₂ , were mixed in an autoclave. The concentration in the autoclave was adjusted by adding water until it was 0.7 lb / gal. The reaction was continued for two hours, then the autoclave was cooled and the product was treated as in Example 1. The reaction temperature was kept constant at 233 ° C. The reaction mixture was agitated by means of a magnetically-driven motor mounted on the autoclave at a constant speed of 600 rpm. The final product was tested for the key parameters; the reaction conditions and the most important pigment properties are shown in Tables 4a and 4b, respectively.

Example 7: Change in the CaO / SiO ₂ mole ratio (XPC 132)

In this example all reaction parameters were kept constant as in Example 4, only the CaO / SiO ₂ molar ratio was increased to 1.6. The hydrothermal reaction was carried out with the same heating and cooling cycle as in the previous examples and the final product was again tested for the most important pigment properties. The reaction conditions and the most important pigment properties are reproduced in Tables 4a and 4b, respectively.

Example 8: Change in the CaO / SiO ₂ mole ratio (XPC 134)

Again, the reaction parameters were again all kept constant as in Example 4, only the CaO / SiO ₂ molar ratio was increased to 1.8. The hydrothermal reaction was carried out with the same heating and cooling cycle as in the previous examples and the final product was again tested for the most important pigment properties. The reaction conditions and the most important pigment properties are reproduced in Tables 4a and 4b, respectively.

Table 4a:

Table 4b:

It should be noted that at a CaO / SiO ₂ molar ratio of 1.6, the calcium silicate hydrate having the highest water absorbency was recovered.

Example 9: Change the reaction time (XPC 172)

In In this example all process conditions became constant as in example 7 kept except the reaction time, which was shortened to one hour. The calcium silicate hydrate complex was tested as in the previous examples and the reaction conditions and the most important pigment properties are shown in Tables 5a or 5b reproduced.

Example 10: Change the reaction time (XPC 173)

In In this example all process conditions were kept constant as in Example 9 except the reaction time, which was extended to 2 hours. The calcium silicate hydrate complex was tested as in the previous examples and the reaction conditions and the most important pigment properties are shown in Tables 5a or 5b reproduced.

Example 11: Change the reaction time (XPC 174)

In In this example all process conditions were kept constant as in Example 9 except the reaction time, which was extended to 3 hours. The calcium silicate hydrate complex was tested as in the previous examples and the reaction conditions and the most important pigment properties are shown in Tables 5a or 5b reproduced.

Table 5a:

Table 5b:

It It should be noted that with a reaction time of 2 hours the Product with the highest whiteness was won. The longer one Reaction time of 3 hours yielded the highest water absorption values, but with less whiteness.

Example 12: Change in concentration of CaO-SiO ₂ slurry (XPC 136)

In this example, all reaction conditions were kept constant as in Example 7 except for the CaO / SiO ₂ slurry concentration, which was lowered to 0.4 lb / gal. First 49.6 g of lime were quenched, sieved and titrated to the available CaO. Then, 34.2 g of ultrafine calcined diatomaceous earth was slurried. The slurry of fluxed calcined kieselguhr was added to the lime slurry such that the mixture had an initial CaO / SiO ₂ molar ratio of 1.6. Then, the starting materials of the reaction were placed in a 2-liter autoclave, and water was added so much that the final concentration of the CaO + SiO ₂ slurry was 0.4 lb / gallon. The reaction temperature was adjusted to 233 ° C. The autoclave was equipped with a temperature controller for the heating and cooling cycle as in 9 presented and regulated. The reaction of the silica-lime slurry was continued for two hours at 233 ° C. At the end of the reaction, the resulting calcium silicate hydrate was cooled by passing water through the jacketed autoclave. The resulting mass was placed in a beaker. The product was tested for the same key parameters as Example 3 using the methods described in Example 3. The reaction conditions and the most important pigment properties are shown in Tables 6a and 6b, respectively.

Example 13: Change in Concentration of CaO-SiO ₂ slurry (XPC 138)

In In this reaction all reaction parameters were kept constant as in Example 12 except the concentration of CaO + SiO 2 slurry, which is at 0.6 lb / gallon was raised. The product was tested as in Example 3 and the reaction conditions and the most important pigment properties are shown in Tables 6a and 6b, respectively.

Example 14: Change in concentration of CaO-SiO ₂ slurry (XPC 140)

In In this reaction all reaction parameters were kept constant as in Example 12 except the concentration of the CaO + SiO 2 slurry, which is at 0.8 lb / gallon was raised. The product was tested as in Example 3 and the reaction conditions and the most important pigment properties are shown in Tables 6a and 6b, respectively.

Example 15: Change in concentration of CaO-SiO ₂ slurry (XPC 141)

In In this reaction all reaction parameters were kept constant as in Example 12 except the concentration of the CaO + SiO 2 slurry, which is at 0.9 lb / gallon was raised. The product was tested as in Example 3 and the reaction conditions and the most important pigment properties are shown in Tables 6a and 6b, respectively.

Table 6a:

Table 6b:

It It should be noted that the slurry concentration of 0.8 lb / gal the highest whiteness and the lowest bulk density brought forth.

 Example 16 (5XPC 52)

In this example, the same procedures described in Example 1 were used, except that the silicon-containing raw material was changed. Instead of kieselguhr, a source of 100% pure silica was used (trade name: Min-U-Sil). The reaction was carried out at a very low concentration of 0.2 lb / gal CaO-SiO ₂ slurry. The resulting calcium silicate hydrate complex was tested for the same main pigment properties as in Example 1. The reaction conditions and the most important pigment properties are shown in Tables 7a and 7b, respectively.

Example 17 (5XPC 55)

In this example, the same procedures described in Example 16 were used (including the use of pure silica as the source of silicon-containing material). The only difference here was that the concentration of CaO-SiO ₂ slurry was increased to 0.4 lb / gallon. The temperature was maintained at 232 ° C. The calcium silicate hydrate complex resulting from this reaction was tested as in Example 16. The reaction conditions and the most important pigment properties are shown in Tables 7a and 7b, respectively.

Table 7a:

Table 7b:

Example 18 Sodium silicate (5XPC 57)

In this example, all the reaction procedures were kept constant as in Example 1. The only difference was the addition of another silicon-containing precursor. Here, 20 parts of fluxed calcined diatomaceous earth was replaced with liquid sodium silicate so that the Na ₂ O-SiO ₂ ratio became 1: 3 (product "N" of the manufacturer PQ) .The total molar ratio of CaO / SiO ₂ was maintained at 1.31 , the concentration of the CaO-SiO ₂ slurry was 0.5 lb / gallon and all other reaction conditions were maintained as well.This product was also tested according to the methods described in Example 1. The reaction conditions and the most important pigment properties are shown in Tables 8a and 8b, respectively 8b.

Table 8a:

Table 8b:

It is to mention that the biggest difference between this product and the previous example in here achieved high whiteness values lies.

Example 19 (CSH of the mark TiSil compared to PCC)

Use of a multiphase calcium silicate hydrate complex containing predominantly foshagite, Ca ₄ (SiO ₃ ) ₃ (OH) ₂ and some xonotlite, Ca ₆ Si ₆ O ₁₇ (OH) ₂ in papermaking with the following process conditions. My novel calcium silicate hydrate complex, which I call CSH brand TiSil, has been used in the manufacture of handsheets. It was compared to commercial PCC (Albacar from SMI (HO)) and a mixture of PCC and about 60 lb / t TiO ₂ . The results of the tests are shown in Tables 9a and 9b. The graphs showing the performance of TiSil compared to PCC are in the 6 to 13 played. The improvement by TiSil compared to PCC is shown in Table 9c. CSH brand TiSil resulted in the following improvements at 20% ash and whiteness:

Table 9a:

Table 9b:

Table 9c:

The CSS pigment of the brand TiSil apparently causes improvements in a combination of properties that were previously unattainable were. So far, for example, usually the porosity the leaves back, when the volume has been improved. In addition, the optical Properties significantly worse when the increased volume due to larger particles was achieved. The unique composition and structure of my novel pigment allows However, the improvement of several key paper properties such as the increase in volume and the reduction in porosity.

Example 20 (CSH brand TiSil compared to PCC at 60 lb / t TiO ₂ )

In this example, the calcium silicate hydrate from Example 1 (5XPC12) was compared to a mixture of Albacar (HO) from SMI containing 60 lbs TiO ₂ per ton. The results of the paper tests are shown in Tables 10a and 10b. The graphical representation of the data is in the 18 to 25 to find. The improvements by TiSil compared to the PCC + TiO ₂ blend (at 20% ash content and whiteness) are given in Table 10c.

Table 10a:

Table 10b:

Table 10c:

CSH The brand TiSil shows here an excellent Lichtstreuvermögen, a unusual Ability, close the sheet (increased Gurley porosity) and a significant improvement in leaf volume, stiffness and the tensile index.

Example 21 (CSH of the mark TiSil vs. Bulkite - XPC65)

In this example, the pigment of my invention, a calcium silicate hydrate complex (foshagite-xonotlite complex), was prepared under the conditions given in Table 11a. The pigment was tested for whiteness, water absorption, Blaine's and pH. The results are shown in Table 11b. This product was compared as a pigment for papermaking with commercial calcium silicate (trade name Bulkite). The graphical representation of the results is in the 26 - 30 played. The comparison of the two pigments, XPC-65 and Bulkite, with an ash content of 20% can be found in Table 11 c. The improvements compared to Bulkite at 20% ash content (interpolated) are given in Table 11d.

Table 11a:

Table 11b:

Table 11c:

Table 11d:

Also This product again shows a significant improvement over the Standard pigments of the industry.

example 22 (XPC 117) Application in Newsprint In this example was the multiphase CSH Foshagit-Xonotlit by the same method as in Example 1 and using the process conditions in Table 12a made.

Table 12a:

The Product was based on its whiteness, water absorption, Blaine values and pH. The results are shown in Table 12b.

Table 12b:

The calcium silicate hydrate complex of this invention was added to the starting material for the production of newsprint (20% kraft pulp, 80% TMP). To compare the performance of the product I invented with other products, handsheets were made with a commercial calcium silicate (Hubersil, JM Huber Co.) and a precipitated calcium carbonate (also from JM Huber Co). The newsprint sheets containing these pigments were tested for the following properties:
Sheet volume, stiffness, porosity, smoothness, whiteness, opacity and various print quality parameters such as strike through, bleed through, and overall print through of the ink. The sheets were also tested for static coefficient of friction.

The actual values interpolated to an ash content of 6% are given in Tables 12c and 12d. A comparison between the product invented by me and Huber's PCC and HuberSil revealed the differences reported in Tables 12e and 12f. The corresponding bar graphs interpolated to an ash content of 6% are in the 31 to 39 shown.

Table 12c:

Table 12d:

Table 12e:

One Comparison of my new multiphase CSH products with the calcium silicate von Huber made the following improvements:

Table 12f:

Also Here, my multiphase CSH product again produces better paper and printing properties than the currently commercially available calcium carbonate and the commercial ones Calcium silicate fillers.

Testing of my novel multiphase calcium silicate hydrate products followed conventional industry standards for quality control. The whiteness was measured using a GE / TAPPI whiteness meter, model S-4. When the pH was measured, this was done with a pH measuring device according to the TAPPI method T-667. The crushing of pulp was carried out by means of a Valley grinding machine according to the TAPPI method T-200. The handsheets were made using a British laboratory sheet mold according to the TAPPI method T-205. To test the handsheets for tensile strength, a one inch strip was used; by the way, the test was carried out according to the TAPPI method T-220. As far as the freeness was measured, this was done by means of a standard Canadian grinder-measuring device according to the TAPPI standard T-227. Ashing tests were carried out at 500 ° C according to the TAPPI method T-211. Air permeability was tested using the Blaine ASTM Method C204. The available lime was measured according to the ASTM method C25. For testing fine paper, a standard pulp of 75% hardwood and 25% softwood was made. The two types of pulp were separately ground to a specific Canadian freeness of 450 ± 10 in a Valley milling machine according to the TAPPI test methods T-200 and T-227. For testing newsprint, a standard newsprint pulp was made from 20% softwood kraft paper and 80% thermomechanical pulp. Both types of pulp were obtained with standard Kandic freeness values of 180 csf ± 25. This freeness was considered sufficient and the pulp was not further ground. To dissolve the pulp, hot water was added to help relax the pulp fibers and avoid fiber lumps in the produced sheets. From the starting material prepared as described, laboratory sheets were formed on a British 6 "laboratory sheet in accordance with the TAPPI Test Method T-205. Since these handsheets were made to test the performance of the fillers, some filler was added to the handsheets in different replacements (typically 15%, 20% and 25%). In order to achieve comparability between the different replacement quantities, a constant basis weight was achieved by reducing the fiber content. That is, a sheet of 25% filler contained only 75% of the fiber content of a non-filled sheet. A retention aid was also used to keep the filler in the sheet until completely dry. All other components in making the handsheets corresponded to the TAPPI T-205 test method. Sheets containing titanium dioxide in fine paper were similarly shaped except that twice as much retention aid was needed as with the other fillers. In addition, when TiO _{2 was used} in conjunction with another filler, TiO _{2 had to be} added first, followed by a dose of retention aid and then the filler and a second dose of retention aid. Newsprint paper sheets were made by a similar method to the fine paper handsheets. However, other filler addition levels were used. For the newsprint sheets, 3%, 6% and 9% filler were usually added. The handsheets were tested according to the TAPPI T-220 test method except that a 25.4 mm sample was used and the tensile index values converted accordingly. The handsheets were ashed according to the TAPPI test method T-211.

Summarized The unique crystalline microfibers exist as a product the reactions described herein arise in a unique manner Product in the form of bundles with a size of approx. 10 to about 40 microns, usually in the form of haystacks or bullets occur. The individual fibers preferably measure in the largest diameter about 0.2 microns and have a length up to 4 or 5 microns, so they have a relatively large L / D ratio.

One important circumstance is that the above-described crystalline Microfibers develop positive properties when used as fillers used in paper, especially in uncoated and coated Wood pulp and in uncoated and coated fine paper. The already mentioned Adsorption properties contribute to the papers being the printing ink take up. Furthermore they help the paper sheet to adsorb fines so that the Total retention capacity the leaves improved in the papermaking process. Overall wise the final paper products improved porosity, smoothness, volume and rigidity on. The whiteness and the opacity are maintained or improved. In addition, the printability of the final product due to the improved ink adsorption significantly improved.

It is obvious that my unique, lightweight, fluffy adsorptive calcium silicate hydrate products and their method of manufacture, as well as the paper products in which they are used, each represent a significant improvement in the art of papermaking. Although only a few exemplary embodiments of this invention have been presented in detail, those that come with Those skilled in the art will recognize that the process and products manufactured thereby can be modified from these embodiments without departing substantially from the novel knowledge and advantages attained thereby.

It It is therefore apparent that the above objectives, including those of which result from the present description, achieved efficiently were. Because certain changes on the way of making the CSH products and the unique Paper products made with their help can be It is understood that my invention in other specific forms can be expressed without a departure from the spirit or the essential features of the invention is present. There can be many other embodiments to be used using the herein disclosed principle to achieve advantageous results. It is therefore understood that the above descriptions of the representative embodiments the inventions for illustrative purposes only and for clarity of the invention have been reproduced. They should not be a full list and no restriction represent and they do not limit the invention to the exact Embodiments, which were revealed. It's all about changes, equivalents and alternatives to be included, by the scope and the spirit covered by the invention, as in the above text and in the attached claims are described. The requirements as such, the products, processes, methods and equivalent Include processes and methods. The scope of the invention described herein The invention is thus intended to also variations of the aforementioned embodiments lock in, by the general scope of meaning and the range of the The terms used herein are those covered and those herein used terms or their legal equivalents become.

ANNEX 1 - DIRECTORY THE PICTURES

1 : 1 shows the X-ray diffraction pattern for the calcium silicate hydrate brand TiSil.

2 : 2 shows the SEM photo of the calcium silicate hydrate brand TiSil with 10,000 times magnification.

3 : 3 shows the SEM photo of the calcium silicate hydrate brand TiSil with 2,000 times magnification.

4 : 4 shows the X-ray diffraction pattern for the calcium silicate hydrate brand StiSil.

5 : 5 shows the SEM photo of the calcium silicate hydrate brand StiSil with 10,000 times magnification.

6 : 6 shows the SEM photo of the calcium silicate hydrate brand StiSil with 2,000 times magnification.

7 : 7 shows a graphical representation of the solubility of lime in water.

8th : 8th shows a graphical representation of the solubility of silica in water.

9 : 9 shows a graphical representation of a standard heating / cooling cycle for the reaction process.

10 : 10 Figure 4 is a graph of whiteness results for handsheets containing TiSil brand calcium silicate hydrate and a commercial grade PCC.

11 : 11 Figure 4 is a graph of the opacity results for handsheets containing the TiSil brand calcium silicate hydrate and a commercial grade PCC.

12 : 12 Figure 4 is a graph of results for the scattering coefficient of the handsheet blades containing the TiSil brand calcium silicate hydrate and a commercial PCC.

13 : 13 Figure 4 is a graphical representation of filler scattering coefficient results for handsheets containing TiSil brand calcium silicate hydrate and a commercial grade PCC.

14 : 14 shows a graphical representation of the sheet stiffness results for lab sheets, containing the calcium silicate hydrate brand TiSil and a commercial PCC.

15 : 15 Figure 4 is a graph of leaf volume results for handsheets containing TiSil brand calcium silicate hydrate and a commercial grade PCC.

16 : 16 Figure 4 shows a graph of porosity results for handsheets containing TiSil brand calcium silicate hydrate and a commercial grade PCC.

17 : 17 Figure 10 is a graph of tensile strength index results for handsheets containing TiSil brand calcium silicate hydrate and a commercial grade PCC.

18 : 18 Figure 4 shows a graph of whiteness results for handsheets containing the TiSil brand calcium silicate hydrate and a PCC with a 60 lb / t TiO ₂ mixture.

19 : 19 Figure 10 shows a plot of the opacity results for handsheets containing the TiSil brand calcium silicate hydrate and a PCC with a 60 lb / t TiO ₂ mixture.

20 : 20 Figure 4 shows a graph of results for the leaves' spread coefficient for handsheets containing the TiSil brand calcium silicate hydrate and a PCC with 60 lb / t TiO ₂ mixture.

21 : 21 Figure 4 shows a graph of results for the scattering coefficient of the filler for handsheets containing the TiSil brand calcium silicate hydrate and a PCC with 60 lb / t TiO ₂ mixture.

22 : 22 Figure 4 is a graph of sheet stiffness results for handsheets containing the TiSil brand calcium silicate hydrate and a PCC with a 60 lb / t TiO ₂ mixture.

23 : 23 Figure 4 is a graph of leaf volume results for handsheets containing the TiSil brand calcium silicate hydrate and a PCC with a 60 lb / t TiO ₂ mixture.

24 : 24 Figure 4 shows a graph of the porosity results for handsheets containing the TiSil brand calcium silicate hydrate and a PCC with a 60 lb / t TiO ₂ mixture.

25 : 25 Figure 1 is a graph of Tensile Index Results for handsheets containing the TiSil brand calcium silicate hydrate and a PCC with a 60 lb / t TiO ₂ mixture.

26 : 26 Figure 4 is a graph of the opacity results for handsheets containing the TiSil brand calcium silicate hydrate and bulk.

27 : 27 Figure 4 shows a graph of results for the scattering coefficient of the leaves for handsheets containing the TiSil brand calcium silicate hydrate and Bulkite.

28 : 28 Figure 4 is a graph of results for the scattering coefficient of the filler for handsheets containing the TiSil brand calcium silicate hydrate and Bulkite.

29 : 29 Figure 4 is a graph of whiteness results for handsheets containing TiSil brand calcium silicate hydrate and bulk.

30 : 30 Figure 4 shows a graph of the porosity results for handsheets containing the TiSil brand calcium silicate hydrate and Bulkite.

31 : 31 Figure 4 is a graph of the opacity results for newsprint handsheets containing 6 (interpolated) TiSil brand calcium silicate hydrate, HuberSil, and Huber carbonate.

32 : 32 Fig. 12 is a graph showing the ink penetration depth data for newsprint handsheets containing 6% (interpolated) of TiSil brand calcium silicate hydrate, HuberSil and Huber carbonate.

33 : 33 shows a graphical representation of the results for show through for Zeitungspa pier lab sheets containing 6 (interpolated) calcium silicate hydrate of the brand TiSil, HuberSil and Huber carbonate.

34 : 34 Figure 4 is a graph of the results of throughprinting for newsprint handsheets containing 6 (interpolated) TiSil brand calcium silicate hydrate, HuberSil and Huber carbonate.

35 : 35 Figure 4 shows a graph of sheet porosity results for newsprint handsheets containing 6 (interpolated) TiSil brand calcium silicate hydrate, HuberSil, and Huber carbonate.

36 : 36 Figure 10 is a graph of Tensile Index Results for newsprint handsheets containing 6% (interpolated) of TiSil brand calcium silicate hydrate, HuberSil, and Huber carbonate.

37 : 37 Figure 4 is a graph showing sheet stiffness results for newsprint handsheets containing 6 (interpolated) TiSil brand calcium silicate hydrate, HuberSil, and Huber carbonate.

38 : 38 Figure 4 is a graph showing static coefficient of friction results for newsprint handsheets containing 6% (interpolated) of TiSil brand calcium silicate hydrate, HuberSil and Huber carbonate.

39 : 39 Fig. 12 is a graph showing the sheet smoothness results for newsprint handsheets containing 6 (interpolated) TiSil brand calcium silicate hydrate, HuberSil, and Huber carbonate.

Claims (11)

Method for improving the opacity of Drying of a mixture of an aqueous pulp and preselected fillers made paper, in which one in the mixture a Foshagit and Incorporating xonotlite containing multiphase calcium silicate hydrate, wherein the multiphase mixture is a fibrous crystalline structure with Foshagit having a diameter of about 0.1 to about 0.2 microns and a length ranging from about 2 microns to about 5 microns and xonotlite particles with a diameter of about 0.1 to 0.3 microns and a length of about 1 micron to about 3 microns. The method of claim 1, wherein the multiphase Calcium silicate hydrate has a water absorption of at least 400 percent up to 1000 percent, preferably from 500 percent to 800 percent, and a unique X-ray diffraction pattern with a first calcium silicate hydrate component having a large peak at d = 2.97 Å, a medium sized Peak at d = 2.31 Å and a small peak at d = 5.05 Å and a second calcium silicate hydrate component with a great Peak at d = 3.11 Å, a medium sized Peak at d = 1.75 Å and a small peak at d = 3.66 Å. The method of claim 1 or 2, wherein the multiphase Calcium silicate hydrate a stable secondary particle with an interlocking Structure of fibrous primary crystals and a porous one haystack-like structure with a mean diameter of about 10 to 40 microns. Method according to one of the preceding claims, in the percentage of Foshagit at least seventy (70) to ninety (90) percent. A method according to any one of the preceding claims wherein the multiphase calcium silicate hydrate is a product of a hydrothermal reaction of an aqueous suspension of lime and a siliceous material in a CaO / SiO ₂ mole ratio of between 1.2: 1 and 1.7: 1, preferably 1, 35 to 1, included. Paper composition with an effective amount of a filler, which is a foshagite and xonotlite-containing multiphase calcium silicate hydrate comprises wherein the multiphase mixture is a fibrous crystalline structure with Foshagit having a diameter of about 0.1 to about 0.2 microns and a length ranging from about 2 microns to about 5 microns and xonotlite particles with a diameter of about 0.1 to 0.3 microns and a length of about 1 micron to about 3 microns. A paper composition according to claim 6, wherein said multiphasic calcium silicate hydrate has a water absorption of at least 400 percent to 1000 percent, preferably from 500 percent to 800 Percent, and a unique X-ray diffraction pattern with a first calcium silicate hydrate component having a large peak at d = 2.97 Å, a medium sized Peak at d = 2.31 Å and a small peak at d = 5.05 Å and a second calcium silicate hydrate component with a great Peak at d = 3.11 Å, a medium sized peak at d = 1.75 Å and a small peak at d = 3.66 Å. Process for preparing a by combining an effective amount of a multiphase calcium silicate hydrate and an aqueous starch solution a coating composition prepared highly absorbent coating formulation for facilitating the printing of a paper substrate, in which contains the multiphase calcium silicate hydrate Foshagit and xonotlite, wherein the multiphase blend with a fibrous crystalline structure Foshagite with a diameter of about 0.1 to about 0.2 microns and a length in the Range from about 2 microns to about 5 microns and xonotlite particles with a diameter of about 0.1 to 0.3 microns and a length of about 1 micron to about 3 microns. The method of claim 8, wherein the multiphase Calcium silicate hydrate has a water absorption of at least 400 percent up to 1000 percent, preferably from 500 percent to 800 percent, and a unique X-ray diffraction pattern with a first calcium silicate hydrate component having a large peak at d = 2.97 Å, a medium sized Peak at d = 2.31 Å and a small peak at d = 5.05 Å and a second calcium silicate hydrate component with a great Peak at d = 3.11 Å, a medium sized Peak at d = 1.75 Å and a small peak at d = 3.66 Å. slurry of calcium silicate hydrate, consisting essentially of those in secondary particles of Calcium silicate intermeshing and dispersed in water fibrous primary crystals according to claim 1. slurry calcium silicate crystals according to claim 10, wherein at least about 95% of the secondary particles an outer diameter less than 40 microns, preferably 10 to 40 microns.