WO1989012032A2

WO1989012032A2 - Process for decomposing an inorganic fiber

Info

Publication number: WO1989012032A2
Application number: PCT/US1989/002288
Authority: WO
Inventors: Leonard Elmo Olds; William Henry Kielmeyer
Original assignee: Manville Sales Corporation
Priority date: 1988-06-01
Filing date: 1989-05-25
Publication date: 1989-12-14
Also published as: WO1989012032A3; CA1338340C; AU3765789A

Abstract

Inorganic fibers which have a silicon extraction of greater than 0.02 wt% Si/day in physiological saline solutions. The fiber contains SiO2, MgO, CaO, and at least one of Al2O3, ZrO2, TiO2, B2O3, iron oxides, or mixtures thereof. Also disclosed are inorganic fibers which have diameters of less than 3.5 microns and which pass the ASTM E-119 two hour fire test when processed into a fiber blanket having a bulk density in the range of about 1.5 to 3 pcf.

Description

PROCESS FOR DECOMPOSING AN INORGANIC FIBER - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

FIELD OF INVENTION

This invention relates to inorganic fiber compositions and more particularly it relates to inorganic fiber compositions which can contain silica, magnesia, calcium oxide, alumina, and other oxides. Some of the inventive fibers have excellent fire ratings, some have especially low durabilities in physiological saline solutions, and some have combinations of these foregoing properties.

BACKGROUND OF THE INVENTION

For many years, inorganic fibers generically referred to in the industry as "mineral wool fibers", made from slag, rock, fly ash, and other by-product raw materials have been manufactured. These fibers have been typically manufactured by melting the slag, rock, etc., containing such oxides as silica, alumina, iron oxide (ferrous and ferric), calcium oxide, and magnesia; allowing the molten material to be blown by gas or steam or to impinge on rotors at high speeds; and causing the resulting blown or spun fibers to be accumulated on a collecting surface. These fibers are then used in bulk or in the form of mates, blankets, and the like as both low and high temperature insulation. U.S. Patent No. 2,576,312 discloses a conventional mineral wool composition and method for making the same.

In the past, the industry has well recognized the standard drawbacks associated with conventional mineral wool fibers. Conventional mineral wool fibers may have high contents of undesired oxides which often detract from their refractory properties. The conventional mineral wools are coarse, i.e. they have average fiber diameters of 4 to 5 microns (measured microscopically) and have high shot contents in the range of 30 to 50 weight percent. The coarseness of the fiber reduces the insulating value of the fiber and makes conventional mineral wool unpleasant to handle and unfriendly to the touch. For example, because of their coarse fiber diameters, conventional mineral wool blankets must have bulk densities of from 4 to 8 pcf and even higher in order to pass the ASTM E-119 two hour fire test. On the other hand, fiber glass blankets are often made with bulk densities of 2 pcf or lower. While the fiber glass blankets are friendly because of their low bulk densities and relatively fine fiber diameter, they do not have sufficient fire resistance so as to pass even the one hour ASTM E-119 fire test.

Recently, another potential problem with traditional mineral wool and other types of fiber has been recognized. It is well known that inhalation of certain types of fiber can lead to elevated incidence of respiratory disease, including cancers of the lung and surrounding body tissue. Several occurrences are welldocumented in humans for several types of asbestos fiber. Although for other varieties of natural and manmade mineral fiber direct and unequivocal evidence for respiratory disease is lacking, the potential for such occurrence has been inferred from results of tests on laboratory animals. In the absence or insufficiency of direct human epidemiological data, results from fiber inhalation or implantation studies on animals provides the best "baseline information" from which to extrapolate disease potential. Chronic toxicological studies on animals have, however, been able to statistically demonstrate the importance of three key factors that relate directly to the potential for respiratory disease and especially carcinoma: (a) dose of fiber received (including time of exposure); (b) dimension of the inhaled fiber; and (c) persistence of the fiber within the lung. The effects of dose and dimension have been well-characterized from such studies and as a result are fairly well known in regard to human disease potential. The dose is obviously a product of the environment in which the fiber is used and the manner in which it is used. The dimension and persistence of the fiber within the lung, on the other hand, are functions of the manner in which the fiber is formed and of its chemical composition. In general, the smaller the fiber the more likely that it will become embedded in lung tissue when inhaled, thus increasing the danger of respiratory disease.

Although less is known about the link between persistence of the fiber within the lung and respiratory disease, increasing attention is being focused on this aspect of the health issue. Biological persistence refers to the length of time a fiber endures as an entity within the body. The physiochemical concept that most closely relates to persistence and is perhaps more easily quantified is that of "durability" - specifically, the chemical solubility (or resistance to solubility) of fibers in body fluids and the tendency of such fibers to maintain physical integrity within such an environment. In general, the less durable a fiber is, the less will be the potential health risk associated with the inhalation of that fiber. One method of measuring the chemical durability of a fiber in body fluids is to measure its durability in physiological saline solutions. This can be done by quantifying the rate of extraction of a chemical component of the fiber such as silicon into the physiological saline solution over a certain period of time.

Thus, as can be easily concluded from the foregoing discussion, conventional mineral wool fibers have several serious drawbacks. However, even the alternatives to mineral wools have problems. For example, as mentioned earlier glass fibers have a fire resistance problem and whereas the refractory ceramic fibers have been gaining increasing use in recent years as an alternative to mineral wool fibers because of their ultra-high temperature resistance and superior ability to pass all fire rating tests, their use is limited by the fact that they are relatively expensive and have a relatively high chemical durability in physiological saline solutions as well.

In conclusion, there is a great need in the industry for low cost, friendly feeling low bulk density inorganic fibers which have good fire resistance properties as measured by their ability to pass the ASTM E-119 two hour fire test. Additionally, there is a tremendous demand for fibers which have especially low durabilities in physiological saline solutions. What would be particularly advantageous to the industry would be fibers with combinations of the above mentioned sought after properties. Also, advantageous would be fibers which also have excellent refractory properties as well, e.g. high continuous service temperatures. SϋMMARY OF THE INVENTION

In one embodiment of the present invention, there are provided inorganic fibers having a silicon extraction of greater than about 0.02 wt% Si/day in physiological saline solutions and a composition consisting essentially of about 0-10 wt% of either Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides, or mixtures thereof; 35-70 wt% SiO₂; 0-50 wt% MgO; and CaO.

In another embodiment of the present invention, there are provided inorganic fibers which have a 5 hour silicon extraction in physiological saline solutions of at least about 10 ppm. These fibers can broadly have compositions consisting essentially of the following ingredients at the indicated weight percentage levels:

0-1.5 wt% of either AI₃O₃, ZrO₂, TiO₂, B₂O₃, iron oxides, or mixtures thereof; 40-70 wt% SiO₂; 0-50 wt% MgO; and CaO

1.5-3 wt% of eitherAl₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides, or mixtures thereof; 40-66 wt% SiO₂; 0-50 wt% MgO; and CaO

3-4 wt% of either Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides, or mixtures thereof; 40-64 wt% SiO₂; 0-50 wt% MgO; and CaO 4-6 wt% of either Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides, or mixtures thereof; 40-59 wt% SiO₂; 0-25 wt% MgO; and CaO

6-8 wt% of either Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides, or mixtures thereof; 35-54 wt% SiO₂; 0-25 wt% MgO; and CaO

8-10 wt% of either Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides, or mixtures thereof; 35-45 wt% SiO₂; 0-20 wt% MgO; and CaO In a preferred embodiment, inventive fibers with 5 hour silicon extractions of greater than about 20 ppm and most preferably greater than about 50 ppm are provided.

In another embodiment of the present invention there are provided inorganic fibers having a diameter of less than 3.5 microns and which pass the ASTM E-119 two hour fire test when processed into a fiber blanket having a bulk density in the range of about 1.5 to 3 pcf and having a composition consisting essentially of about: 0-10 wt% of either Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides, or mixtures thereof; 58-70 wt% SiO₂; 0-21 wt% MgO; 0-2 wt% alkali metal oxides; and CaO and wherein the amount of alumina + zirconia is less than 6 wt% and the amount of iron oxides or alumina + iron oxides is less than 2 wt%. Preferably, the inventive fibers in this embodiment may have compositions consisting essentially of about:

0-1.5 wt% of either Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides, or mixtures thereof; 58.5-70 wt% SiO₂; 0-21 wt% MgO; 0-2 wt% alkali metal oxides; and CaO greater than 1.5 wt% up to and including 3 wt% of either Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides, or mixtures thereof; 58.5-66 wt% SiO₂; 0-21 wt% MgO; 0-2 wt% alkali metal oxides; and CaO greater than 3 wt% up to and including 4 wt% of either Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides, or mixtures thereof; 58-63 wt% SiO₂; 0-8 wt% MgO; 0-2 wt% alkali metal oxides; and CaO greater than 4 wt% up to and including 6 wt% of either Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides, or mixtures thereof; 58-59 wt% SiO₂; 0-7 wt% MgO; 0-2% alkali metal oxides; and CaO. As discussed herein earlier, there has been a demand in the industry for inorganic fibers with an excellent fire rating at low bulk densities and fibers with especially low chemical durabilities in physiological saline solutions. Therefore, each category of inventive fibers should fulfill a real need in the industry and should be available for applications where heretofore low cost, mineral wool type fibers have not been available. What is particularly advantageous about the present invention is the fact that fibers are provided where a special demand exists, i.e. applications in the industry where fibers with both an excellent fire rating and an especially low durability in physiological saline solutions are in demand.

Other features and aspects, as well as the various benefits and advantages, of the present invention will be made clear in the more detailed description which follows.

DETAILED DESCRIPTION OF THE INVENTION

The inventive fiber compositions of the present invention can be made from either pure metal oxides or less pure raw materials which contain the desired metal oxides. Table 1 herein gives an analysis of some of the various raw materials which can be used to make inventive fiber compositions. Physical variables of the raw materials such as particle size may be chosen on the basis of cost, handleability, and similar considerations.

Except for melting, the inventive fibers are formed in conventional inorganic fiber forming equipment and by using standard inorganic fiber forming techniques as known to those skilled in the art. Preferably, production will entail electric furnace melting rather than cupola melting since electric melting keeps molten oxides of either pure or less pure raw materials more fully oxidized thereby producing longer fibers and stronger products. The various pure oxides or less pure raw materials are granulated to a size commonly used for electric melting or they may be purchased already so granulated.

The granulated raw materials are then mixed together and fed to an electric furnace where they are melted by electric resistance melting with electrodes preferably positioned according to the teachings of U.S. Patent No. 4,351,054. Melt formation can be either continuous or batchwise although the former is preferred. The molten mixture of oxides is then fiberized as disclosed in U.S. Patent No. 4,238,213.

While the fiberization techniques taught in U.S. 4,238,213 are preferred for making the inventive fibers, other conventional methods may be employed such as sol-gel processes and extrusion through holes in precious metal alloy baskets.

The fibers so formed will have lengths in the range of from about 0.5 to 20 cm and diameters in the range of from about 0.05 to 10 microns with the average fiber diameter being in the range of about 1.5 to 3.5 microns. Table 2 shows the average fiber diameter

(measured microscopically) and the unfiberized shot content of various inventive fibers. As may be seen, the average microscopic fiber diameter was 2.3 microns and the average unfiberized shot content was 27%. For purposes of comparison, conventional mineral wool fibers were also tested with the results being given in Table 2 as numbers 226 and 229. These conventional fibers averaged 4.7 microns (measured microscopically) in diameter and had an average 40 wt% shot content. The continuous service temperature ranged from 1370°F to 1490°F, averaging 1420°F.

Table 3 contains an extensive chemical analysis of a number of inventive fibers. Because of the large number of fiber samples containing alumina additives made to the base calcium oxide/magnesia/silica system, only the average analysis of the minor constituent of these fibers are given in Table 3. The silica, alumina, magnesia, and calcium oxide contents for these fibers are given in Table 4.

As used herein, the "service temperature" of an inorganic fiber is determined by two parameters. The first is the obvious condition that the fiber must not soften or sinter at the temperature specified. It is this criterion which precludes the use of glass fibers at temperatures about 800°F to 1000°F (425° to 540°C). Additionally, a felt or blanket made from the fibers must not have excessive shrinkage when soaking at its service temperature. "Excess shrinkage" is usually defined to be a maximum of 5% linear or bulk shrinkage after prolonged exposure (usually for 24 hours) at the service temperature. Shrinkage of mats or blankets used as furnace liners and the like is of course a critical feature, for when the mats or blankets shrink they open fissures between them through which the heat can flow, thus defeating the purpose of the insulation. Thus, a fiber rated as a "1500 ºF (815°C) fiber" would be defined as one which does not soften or sinter and which has acceptable shrinkage at that temperature, but which begins to suffer in one or more of the standard parameters at temperatures above 1500°F (815°C).

The service temperatures for a representative number of fibers in the inventive compositional range are listed in Table 2. The continuous service temperature for constant silica/magnesia/calcium oxide ratios are given in Table 6. As may be seen in all cases, the lower the alumina content of the fiber, the higher the service temperature will be, with the highest service temperature being at zero percent alumina for alumina contents less than 30%. Thus to attain the most desired properties of the inventive fiber it is not possible to accept any of the alumina contents resulting from melting the traditional mineral wool raw materials. Rather, various amounts of sufficiently pure oxides will be required to dilute the alumina contents to the desired low levels. To attain fibers of the highest service temperatures, only pure raw materials with essentially no significant amounts of alumina must be used.

A series of inventive fibers were also tested for their silicon extraction in a saline solution according to the following procedure:

A buffered model physiological saline solution was prepared by adding to 6 liters of distilled water the following ingredients at the indicated concentrations: Ingredient Concentration, g/l

MgCl₂6H₂O 0.160

NaCl 6.171 KCl 0.311

Na₂HPO₄ 0.149

Na₂SO_A 0.079

CaCl₂2H₂O 0.060 NaHCO₃ 1.942

NaC₂H₃O₂ 1.066

Before testing, this solution was buffered to a pH of 7.6 by bubbling with a gaseous mixture of 5% CO₂/95%N₂.

One half (1/2) gram of each sample of fiber listed in Table 3 was then placed into separate closed, plastic bottles along with 50 cc of the prepared physiological saline solution and put into an ultrasonic bath for 5 hours. The ultrasonic vibration application was adjusted to give a temperature of 104°F at the end of the 5 hour period. At the end of the test period, the saline solution was filtered and the solution chemically analyzed for silicon content. The silicon concentration in the saline solution was taken to be a measure of the amount of fiber which solubilized during the 5 hour test period. The CaO and MgO contents of the fiber were similarly solubilized.

One of the inventive fibers was tested for silicon extraction in a physiological saline solution for periods of up to 6 months. Results were as follows: Steady State Total Comments On

Silicon Silicon Extraction Amphoteric Fiber Residue

Fiber Extraction Rate For 0.20 m²/g Oxides in After 6

Number in 6 Months Surface Area,% Si/day Fiber Months

29 (inventive) 96% 0.16% 1.0% carbonate hydroxyl apatite fiber, disintegrated into small particles

137 (non- 0.013% 8.9% slight fine grained inventive) fibers with uniform corrosion

235 (non- 0.012% 25.6% no fiber inventive) corrosion; some surface deposition

Categorization of oxides melts according to scales of acidity or basicity has been well known for many years. (See "A Scale of Acidity and Basicity in Glass," Glass Industry, February 1948, pp 73-74.) We have now found that by strictly controlling the compositions of the oxide melts according to the acidic or basicity behavior of the respective oxides, fibers can be made which are surprisingly soluble in saline solutions. Increasing the content of silica, alumina, and the amphoteric oxides in the fiber increases the acid ratio of the fiber composition. This tends to stabilize the system against silicon extraction by weak solutions as a result of relative changes in the interatomic bonding forces and extension of the silica network. Other amphoteric oxides besides alumina will have an alumina equivalency with respect to extraction by saline solutions. The amphoteric oxides zirconia and titania appear to have an alumina equivalency of close to 1 to 1. We have found that in general for desired high saline solubility the amount of total amphoteric oxides must be kept below about 10% depending upon the amount of silica present. On the other hand, with the exception of iron and manganese oxides, the basic oxides can vary widely since their alumina equivalency is small. However, while iron and manganese oxides are generally considered to be basic in nature, their behavior with respect to saline solubility more closely relate to the amphoteric oxides, thus the amounts of iron and manganese oxides must be similarly limited.

Many of the fibers were tested for their fire resistance according to the following simulated fire rating test procedure: For screening test purposes, a small furnace was constructed using an electrically heated flat-plate element at the back of the heat source. A 6 inch × 6 inch × 2 inch thick sample of 1 3/4 to 6 1/2 pcf density of each formulated fiber was mounted parallel with the element and 1 inch from it. Thermocouples were then positioned at the center of the fiber sample surfaces.

A computer was used to control power via a simple on-off relay system to the heating element. The position of the relay was based on the reading of the thermocouple on the sample surface nearest the element and the programmed fire test heat-up schedule.

The furnace was heated so as to follow a standard ASTM E-119 time/temperature curve for the 2-hour test period. In the test utilized herein, failure of the fiber is considered to occur when the furnace is unable to maintain the standard temperature per ASTM E-119 because the fiber insulation has sintered sufficiently to allow heat to escape through the fiber layer.

The results of the testing of the fibers for saline solubility and the two hour ASTM E-119 fire test are given in Table 4 for the fibers made with alumina addition and in Table 5 for the remaining fibers to which other oxidic constituents were added. These additions included: B₂O₃, P₂O₅, TiO₂, ZrO₂, Fe₂O₃ + MnO, La₂O₃, Cr₂O₃, and Na₂O. For glass fibers within the scope of the invention to function in an ASTM E-119 fire test, i.e. to withstand the rising temperatures of a simulated fire which can reach 1850°F in two hours, it is necessary that they convert from an amorphous condition to a beneficial pseudo crystalline state during heat-up. The inventive fibers do this but can be assisted in this function by the inclusion of suitable crystal nucleating agents. Such agents may include TiO₂, ZrO₂, platinum, Cr₂O₃, P₂O₅, and others. Such additions are within the scope of this invention.

TABLE 1 RAW MATERIALS USED

Pure Raw Materials

Silica Quick Calcined Aluminum Magnesium Sand Lime Dolomite Oxide Oxide

ACIDIC OXIDES

SiO₂ 99.0 0.34 0.50 0.02 0.4

AMPHOTERIC OXIDES

TiO₂ nil nil nil 0.002 nil

Al₂O₃ 0.30 0.26 0.50 98.8 0.1

BASIC OXIDES Fe₂O₃ 0.30 0.05 0.15 0.02 0.7

MnO -- -- -- -- --

MgO 0.02 0.14 40.0 nil 96.3

CaO 0.03 97.75 57.0 0.01 2.0

Na₂O 0.04 0.02 0.01 0.30 0.02

K₂O 0.01 0.01 nil 0.01 0.01

MISCELLANEOUS

SO₃ -- -- 0.4 -- --

S⁼ -- -- -- -- --

C -- -- -- --

LOI 0.2 0.7 3.0 0.20 1.8

TOTAL 99.90 99.27 101.56 99.36 101.33

TABLE 1 RAW MATERIALS USED (continued)

Less Pure Raw Materials

Blast Furnace Nepheline

Kaolin Slag Syenite Talc

ACIDIC OXIDES

SiO₂ 50.5 35.16 61.3 61.2

AMPHOTERIC OXIDES

TiO₂ 1.61 0.62 0.003 nil

Al₂O₃ 43.6 12.88 23.4 0.7BASIC OXIDES Fe₂O₃ 0.80 0.20 0.07 0.85

MnO 0.62 -- --

MgO 0.01 16.06 0.05 31.7

CaO 0.04 32.94 0.58 0.19 Na₂O 0.06 0.45 9.60 -- K₂O 0.02 0.25 4.50 --

MISCELLANEOUS

SO₃ -- 0.28 -- --

S⁼ -- 1.03 -- --

C -- 0.30 -- -- LOI 2.90 -- 0.62 5.0 TOTAL 99.54 100.79 100.12 99.0

Silica Sand: Ottawa Silica - Sil-co-Sil Grade 295 Quick Lime: Mississippi Lime - Pulverized Quick Lime Calcined Dolomite: Ohio Lime NO. 16 Burnt Dolomitic Lime Aluminum Oxide: Reynolds Calcined Alumina, RC-23 Magnesium Oxide: Baymag 56 Feed Grade Kaolin: American Cyanamide Andersonville Kaolin Blast Furnace Slag: Calumite Morrisville Slag Nepheline Syenite: Indusmin Grad A400 Talc: Pfizer Grade MP4426

Additives:

Soda Ash: 58.3% Na₂O

Boric Acid: 55.5% B₂O₃

Magnetite Iron Concentrates: 98.5% Iron Oxides

Zircon: 66.2% ZrO₂

Manganese Oxide: 99% MnO₂ Titanium Dioxide: 99% TiO₂

Chromium Oxide: 99.5% Cr₂O₃

Lanthanum Carbonate: Moly Corp.

TABLE 3 COMPOSITION OF FIBERS

ACIDIC OXIDES AMPHOTERIC OXIDES

TEST SUB SUB NO. B₂O₃ SiO₂ P₂O₅ TOTAL TiO₂ Al₂O₃ ZrO₂ TOTAL

Composition of Fibers with Al₂O₃ additions (minor constituents only) 1 to 0.00 -- 0.00 -- 0.01 -- 0.01 0.02 -- -- -- --

Composition of Fibers with B₂O₃ additions

164 0.32 64 .8 -- 65.12 -- 0.06 -- 0.06 165 0.52 63.9 -- 64.42 -- 1.20 -- 1.20 166 0.64 64.6 -- 65.24 -- 0.06 -- 0.06 167 0.82 64.5 -- 65.32 -- 0.06 -- 0.06 168 1.33 64.1 -- 65.43 -- 0.06 -- 0.06 169 1.37 64.1 -- 65.47 -- 0.06 -- 0.06 170 2.22 63.6 -- 65.82 -- 0.06 -- 0.06 171 8.41 59.6 -- 68.01 -- 0.06 -- 0.06

Composition of Fibers with P₂O₅ additions 2 -- 49 .6 6.05 55.65 0.06 0.38 0.04 0.48

Composition of Fibers with TiO₂ additions

173 -- 48.6 48.6 10.0 41.4 -- 51.4 Composition of Fibers with ZrO₂ additions

174 -- 63 .5 63.5 .01 0.88 0.21 1.10 175 -- 59.2 59.2 -- 0.33 0.40 0.73 176 -- 59.5 59.5 -- 0.31 0.42 0.73

TABLE 3 COMPOSITION OF FIBERS (continued) BASIC OXIDES

TEST SUB NO. FeO₃ MnO La₂O₃ Cr₂O₃ MgO Li₂O CaO BaO Na₂O K₂O TOTAL

Composition of Fibers with Al₂O₃ additions (minor constituents only)

1 to 0.06 0.02 0.00 0.02 -- 0.00 -- 0.04 0.04 0.01 .19 -- -- -- -- -- -- -- -- -- --

Composition of Fibers with B₂O₃ additions

164 -- -- -- 8.7 -- 26.6 -- -- -- 35.3 165 -- -- -- 8.6 -- 26.2 -- -- -- 34.8 166 -- -- -- 8.7 -- 26.5 -- -- -- 35.2 167 -- -- -- 8.7 -- 26.5 -- -- -- 35.2 168 -- -- -- 8.6 -- 26.3 -- -- -- 34.9 169 -- -- -- 8.6 -- 26.3 -- -- -- 34.9 170 -- -- -- 8.5 -- 26.1 -- -- -- 34.6 171 -- -- -- 8.0 -- 24.0 -- -- -- 32.0 Composition of Fibers with P₂O₅ additions

2 0.21 0.00 -- 0.68 11.15 0.00 31.45 0.00 0.05 0.04 43.58

Composition of Fibers with TiO₂ additions 173 -- -- -- -- -- -- -- -- -- -- --

Composition of Fibers with ZrO₂ additions

174 -- -- -- -- 0.33 -- 35.55 -- .03 .01 35.92

175 -- -- -- -- 0.41 -- 39.1 -- -- -- 39.51

176 -- -- -- -- 0.42 -- 39.1 -- -- -- 39.52

TABLE 3 COMPOSITION OF FIBERS (continued)

MISCELLANEOUS

TEST SUB NO. SO₃ Misc. TOTAL TOTAL

Composition of Fibers with Al₂O₃ additions (minor constituents only)

1 to .05/ .02 .07/ .14

.20 -- .22 .44 Composition of Fibers with B₂O₃ additions 164 -- -- -- 100.48 165 -- -- -- 100.42 166 -- -- -- 100.5 167 -- -- -- 100.58 168 -- -- -- 100.39 169 -- -- -- 100.43 170 -- -- -- 100.48 171 -- -- -- 100.07 Composition of Fibers with P₂O₅ additions

2 -- 0.02 0.02 99.73

Composition of Fibers with TiQ₂ additions 173 -- -- -- 100.0

Composition of Fibers with ZrQ₂ additions 174 -- -- -- 100.52 175 -- -- -- 99.44 176 -- -- -- 99.75

TABLE 3 COMPOSITION OF FIBERS

ACIDIC OXIDES AMPHOTERIC OXIDES

TEST SUB SUB

NO. B₂O₃ SiO₂ P₂O₅ TOTAL TiO₂ Al₂O₃ ZrO₂ TOTAL

Composition of Fibers with ZrO₂ additions (Cont.)

177 -- 59.7 -- 59.7 -- 0.34 0.50 0.84

8 -- 60.0 -- 60.0 -- 0.36 0.54 0.90

179 -- 59.2 -- 59.2 -- 0.35 0.58 0.93

180 -- 54.3 -- 54.3 .01 1.29 0.58 1.88

181 -- 59.2 -- 59.2 -- 0.32 0.83 1.15

182 -- 46.85 -- 46.85 .02 2.03 0.84 2.89

182(a) -- 59.4 -- 59.4 -- 0.38 2.31 2.69

183 -- 59.05 -- 59.05 -- 0.30 2.65 2.95

184 -- 57.96 -- 57.96 -- 0.42 3.11 3.53

185 -- 57.8 -- 57.80 -- 0.56 3.12 3.68

186 -- 59.05 -- 59.05 -- 0.38 3.27 3.65

187 -- 56.88 -- 56.88 -- 0.32 3.30 3.62

188 -- 57.7 -- 57.7 -- 0.20 3.30 3.50

189 -- 58.19 -- 58.19 -- 0.39 3.36 3.75

190 -- 57.86 -- 57.86 -- 0.36 3.37 3.73

191 -- 58.6 -- 58.6 -- 0.58 3.67 4.25

192 -- 58.4 -- 58.4 -- 0.65 3.69 4.34

193 -- 56.65 -- 56.65 .02 3.35 4.50 7.87

TABLE 3 COMPOSITION OF FIBERS (continued) BASIC OXIDES

Composition of Fibers with ZrO₂ additions (Cont.)

177 -- -- -- 0.46 -- 38.7 -- -- -- 39.16 8 -- -- -- 0.48 -- 38.3 -- -- -- 38.78 179 -- -- -- 0.98 -- 37.0 -- -- -- 37.98 180 .09 .01 -- 10.20 -- 32.75 .01 .04 .02 43.12 181 -- -- -- 1.13 -- 36.6 -- -- -- 37.73 182 .08 .01 -- 20.6 -- 29.2 .03 .05 .01 49.98 182(a) -- -- -- 2.06 -- 34.9 -- -- -- 36.96 183 .06 .00 05 3.08 -- 34.84 .00 .03 .01 38.07 184 -- -- -- 3.55 -- 35.17 -- -- -- 38.72 185 -- -- -- 3.74 -- 34.4 -- -- -- 38.14 186 -- -- -- 2.57 -- 36.94 -- -- -- 39.51 187 -- -- -- 4.00 -- 36.45 -- -- -- 40.45 188 -- -- -- 3.00 -- 36.0 -- -- -- 39.0 189 -- -- -- 3.26 -- 35.39 -- -- -- 38.65 190 -- -- -- 3.22 -- 35.66 -- -- -- 38.88 191 -- -- -- 2.72 -- 33.5 -- -- -- 36.22 192 -- -- -- 2.59 -- 33.2 -- -- -- 35.79 193 .05 .00 .00 3.35 -- 31.9 .00 .05 01 35.36

TABLE 3 COMPOSITION OF FIBERS (continued) MISCELLANEOUS

TEST SUB NO. SO₃ Misc. TOTAL TOTAL

Composition of Fibers with ZrO₂ additions (Cont.) 177 -- -- -- 99 .70 8 -- -- -- 99 .68 179 -- -- -- 98 .11

180 -- .01 .01 99 .31

181 -- -- -- 98.08

182 -- .02 .02 99.74 182(a) -- -- -- 99.05

183 -- .02 .02 100.09 184 -- -- -- 100 .21

185 -- -- -- 99 .62 186 -- -- -- 102 .21 187 -- -- -- 100.95 188 -- -- -- 100.20 189 -- -- -- 100.59 190 -- -- -- 100. 47 191 -- -- -- 99. 07 192 -- -- -- 98. 53 193 -- .01 .01 99. 89

TABLE 3 COMPOSITION OF FIBERS

ACIDIC OXIDES AMPHOTERIC OXIDES

TEST SUB SUB NO. B₂O₃ SiO₂ P₂O₅ TOTAL TiO₂ Al₂O₃ ZrO₂ TOTAL

Composition of Fibers with FeO₃ and MnO additions

194 -- 64.9 -- 64.9 -- 0. ,06 -- 0.06 195 -- 49.8 -- 49.8 .01 18. ,0 .01 18.02 196 -- 50.4 -- 50.4 .03 7. ,45 .01 7.49 197 -- 64.34 -- 64.34 -- 0. ,06 -- 0.06 198 -- 63.70 -- 63.70 -- 1. ,20 -- 1.20 199 -- 63.54 -- 63.54 -- 1. ,20 -- 1.20 200 -- 38.9 -- 38.9 .01 6. ,70 .01 6.72 201 -- 64.3 -- 64.3 -- 0. ,06 -- 0.06 202 -- 44.6 -- 44.6 .01 0. ,92 .01 0.94 203 -- 63.3 -- 63.3 -- 1. ,15 -- 1.15 204 -- 63.6 -- 63.6 -- 0. ,06 -- 0.06 205 -- 43.8 -- 43.8 .01 15. .26 .01 15.28 206 -- 62.3 -- 62.3 -- 1, .20 -- 1.20 207 -- 63.3 -- 63.3 -- 0. .06 -- 0.06 208 -- 43.9 -- 43.9 .01 14. .3 .01 14.32 209 -- 62.0 -- 62.0 -- 0. .06 -- 0.06 210 -- 60.0 -- 60.0 -- 2, .0 -- 2.0 211 -- 60.0 -- 60.0 -- -- -- --

TABLE 3

COMPOSITION OF FIBERS (continued) BASIC OXIDES

TEST SUB

NO. FeO₃ MnO La₂O₃ Cr₂O₃ MgO Li₂O CaO BaO Na₂O K₂O TOTAL

Composition of Fibers with FeO₃ and MnO additions

194 0.06 -- -- -- 8.72 -- 26.6 -- -- -- 35 .38

195 .22 -- -- -- 0.2 -- 31.5 -- -- -- 31.92

196 .48 .04 -- -- 15.2 -- 26.2 -- .07 .05 42 .04

197 .50 -- -- -- 7.80 -- 26.4 -- -- -- 34.7

198 .69 -- -- -- 7.73 -- 25.30 -- -- -- 33.72

199 .72 -- -- -- 7.70 -- 25.04 -- -- -- 33.46

200 .80 -- -- -- 16.1 -- 37.5 -- -- -- 54.40

201 .96 -- -- -- 8.6 -- 26.4 -- -- -- 35 .96

202 1.02 -- -- -- 18.1 -- 32.8 -- -- -- 51.92

203 1.61 -- -- -- 7.98 -- 25.4 -- -- -- 34.99

204 1.92 -- -- -- 8.6 -- 26.1 -- -- -- 36.62

205 2.90 .04 -- .14 22.7 -- 15.05 -- .10 .01 40.94

206 3.05 -- -- -- 8.0 -- 25.0 -- -- -- 36.05

207 3.45 -- -- -- 8.0 -- 25.5 -- -- -- 36.95

208 3.50 -- -- -- 24.4 -- 13.7 -- -- -- 41. 6

209 4.81 -- -- -- 8.0 -- 25.5 -- -- -- 38. 31

210 -- 8.0 -- -- 30.0 -- -- -- -- -- 38. 0

211 -- 20.0 -- -- 20.0 -- -- -- -- -- 40. 0

TABLE 3 COMPOSITION OF FIBERS (continued) MISCELLANEOUS

TEST SUB NO. SO₃ Misc. TOTAL TOTAL

Composition of Fibers with FeO₃ and MnO additions 194 -- -- -- 100.34

195 .05 .02 .07 99.81 196 .05 .02 .07 100.00 197 -- -- -- 99.1 198 -- -- -- 98.62 199 -- -- -- 98.20 200 .05 .02 .07 100.09 201 -- -- -- 100.32 202 -- -- -- 97.46 203 -- -- -- 99.44 204 -- -- -- 100.28 205 .05 .08 .13 100.15 206 -- -- -- 99.55 207 -- -- -- 100.31 208 -- -- -- 99.82 209 -- -- -- 100.37 210 -- -- -- 100.0 211 -- -- -- 100.0

TABLE 3 COMPOSITION OF FIBERS

ACIDIC OXIDES AMPHOTERIC OXIDES

TEST SUB SUB NO. B₂O₃ SiO₂ P₂O₅ TOTAL TiO₂ Al₂O₃ ZrO₂ TOTAL

Composition of Fibers with La₂ O₃ additions -- -- 58.1 -- 58.1 -- 0.06 -- 0.06

213 -- 57.8 -- 57.8 -- 0.06 -- 0.06

214 -- 57.5 -- 57.5 -- 0.06 -- 0.06

215 -- 56.9 -- 56.9 -- 0.06 -- 0.06 Composition of Fibers with Cr₂O₃ additions 216 62.6 -- 62.6 0.01 0.49 0.01 0.51Composition of Fibers with Na₂O additions 17 -- 64.7 -- 64.7 -- 0.06 -- 0.062l8 -- 64.5 -- 64.5 -- 0.06 -- 0.06219 -- 64.4 -- 64.4 -- 0.06 -- 0.06220 -- 63.5 -- 63.5 -- 1.20 -- 1.20 221 -- 64.3 -- 64.3 -- 0.06 -- 0.06

222 -- 64.2 -- 64.2 -- 0.06 -- 0.06

223 -- 64.0 -- 64.0 -- 0.06 -- 0.06

224 -- 63.0 -- 63.0 -- 0.06 -- 0.06

225 -- 60.3 -- 60.3 -- 0.06 -- 0.06

TABLE 3 COMPOSITION OF FIBERS (continued)

BASIC OXIDES

TEST SUB

NO. FeO₃ MnO La₂O₃ Cr₂O₃ MgO Li₂O CaO BaO Na₂O K₂O TOTAL

Composition of Fibers with La₂O₃ additions -- 0.16 -- 0.00 -- 4.60 -- 36.71 -- -- -- 41.47

213 0.15 -- 0.56 -- 4.58 -- 36.53 -- -- -- 41.82

214 0.15 -- 0.72 -- 4.55 -- 36.3 41.72

215 0.15 -- 0.92 -- 4.51 -- 36.0 -- -- -- 41.58 Composition of Fibers with Cr₂O₃ additions

216 0.08 .00 -- 0.09 2.30 -- 34.10 0.00 0.03 0.01 36.61

Composition of Fibers with Na₂O additions

17 -- -- -- -- 8.7 -- 26.6 -- 0.28 -- 35.58

218 -- -- -- -- 8.7 -- 26.5 -- 0.45 -- 35.65

219 -- -- -- -- 8 . 6 -- 26.5 -- 0.71 -- 35.80 220 -- -- -- -- 8 . 5 -- 26.1 -- 0.87 -- 35.70 221 -- — -- -- 8 .5 -- 26.2 -- 0.93 -- 35.63

222 -- -- -- -- 8 . 6 -- 26.4 -- 1.11 -- 36.11

223 -- -- -- -- 8 . 6 -- 26.3 -- 1.40 -- 36.3

224 -- -- -- -- 8 . 5 -- 25.9 -- 2.60 -- 37.0

225 -- -- -- -- 8 . 1 -- 24.8 -- 6.84 -- 39.74

TABLE 3 COMPOSITION OF FIBERS (continued) MISCELLANEOUS

TEST SUB NO. SO₃ Misc. TOTAL TOTAL

Composition of Fibers with La₂ O₃ additions -- -- -- -- 99.63

213 -- -- -- 99.68 214 -- -- -- 99.28 215 -- -- -- 98.54

Composition of Fibers with Cr₂O₃ additions

216 -- -- -- 99.72

Composition of Fibers with Na₂O additions

17 -- -- -- 100.34 218 -- -- -- 100.21 219 -- -- -- 100.26 220 -- -- -- 100.40 221 -- -- -- 99.99 222 -- -- -- 100.37 223 -- -- -- 100.36 224 -- -- -- 100.06 225 -- -- -- 100.1

TABLE 3 COMPOSITION OF FIBERS

ACIDIC OXIDES AMPHOTERIC OXIDES

TEST SUB SUB

NO. B₂O₃ SiO₂ P₂O₅ TOTAL TiO₂ Al₂O₃ ZrO₂ TOTAL

Composition of Conventional Mineral Wools

226 40.0 - 40.0 0.37 9.1 0.03 9.50

39.9 0.02 39.92 1.11 12.85 0.03 13.99

228 37.65 0.84 38.49 2.35 9.85 0.04 12.24 229 41.75 0.12 41.87 1.07 16.0 0.03 17.10

Composition of Refractory Fibers (Fibers with less than 25% Basic Oxides)

231 - 31.0 - 31.0 - 47.5 0.02 47.52 232 - 37.1 - 37.1 - 59.2 - 59.2 233 - 50.0 - 50.0 - 40.0 - 40.0 234 - 54.0 - 54.0 - 46.0 - 46.0 235 - 58.47 1.15 59.62 0.98 24.54 0.03 25.55 236 - 52.1 - 52.1 1.76 44.4 .23 46.39 237 - 52.0 - 52.0 1.71 42.2 2.93 46.84 238 - 49.8 - 49.8 1.60 38.3 9.32 49.22 239 - 48.6 - 48.6 1.55 36.2 12.3 50.05 240 - 47.8 - 47.8 1.50 34.4 15.1 51.00 241 - 46.2 - 46.2 1.40 31.0 20.7 53.10 242 - 28 - 28 19 50 3 72 243 - 64.5 - 64.5 - 27.4 - 27.4

TABLE 3 (cont'd.) COMPOSITION OF FIBERS BASIC OXIDES MISCELLANEOUS

TEST SUB SUB

NO. FeO₃ MnO La₂O₃ Cr₂O₃ MgO Li₂O CaO BaO Na₂O K₂O TOTAL SO₃ Misc. TOTAL TOTAL

Composition of Conventional Mineral Wools

226 0.47 0.64 - 0.02 11.2 0.01 36.5 0.04 0.54 0.55 49.97 0. 1 0. 59 0. 69 100. 16

0.35 0.24 - 0.00 6.05 0.01 38.55 0.12 0.23 0.27 45.82 0. 67 0. 07 0. 74 100. 47

228 9.7 0.22 - 0.04 12.95 0.01 23.55 0.07 2.01 0.80 49.35 0. 42 0. 19 0. 61 100. 69

229 3.75 0.23 - 0.02 6.45 0.63 27.75 0.03 2.04 0.63 41.53 0. 56 0. 08 0 . 64 101 . 14

Composition of Refractory Fibers (Fibers with less than 25% Basic Oxides

231 - - - - - - 1.2 - 20.2 - 21.4 - - - 99.92

232 - - - - - - 0.2 - 3.1 - 3.3 - - - 99.6

233 - - - - - - 5.6 - 4.4 - 10.0 - - - 100

234 - - - - - - - - - - - - - - 100

235 3.70 0.02 - 0.00 1.44 0.02 5.78 0.54 1.55 1.18 14.23 0.47 0.24 0.71 100.11

236 .83 - - - 0.07 - 0.12 - .05 .06 1.13 - - - 99.62

237 .77 - - - 0.07 - 0.12 - .05 .06 1.07 - - - 99.91

238 .72 - - - 0.07 - 0.12 - .05 .06 1.02 - - - 100.04

239 .70 - - - 0.07 - 0.12 - .05 .06 1.00 - - - 99.65

240 .68 - - - 0.07 - 0.12 - .05 .06 .98 - - - 99.78

241 .63 - - - 0.07 - 0.12 - .05 .06 0.93 - - - 100.23

242 - - - - - - - - - - - - - - 100

243 - - - - - 8.4 - - - - 8.4 - - - 100.3

TABLE 4 TEST RESULTS ON FIBERS MADE WITH ALUMINA ADDITIONS

COMPOSITION. WT% 5 Hour

Acidic Amphoteric Saline E-119 Fire Test

Oxides Oxides Basic Oxides Total Extraction Thickness 2 Hour

NO. SiO₂ Al₂O₃ Total CaO MgO Total Analytical ppm. Si Density Test**

0 to 1 1/2% Amphoteric Oxides

1 32 0.2 0.22 39 29 68.1 100.37 * * * 2 31.3 0.2 0.22 33.3 35.5 68.9 100.47 * * *

3 41.9 0.28 0.30 57.5 0.1 57.7 99.95 80 - -

4 43.5 0.33 0.35 46.0 10.4 56.5 100.40 58 - -

5 43.7 0.25 0.27 39.8 16.6 56.5 100.52 46 2.0/1.27 - F

6 45.0 0.50 0.52 54.4 0.1 54.6 100.17 75 - -

7 46.5 0.20 0.22 9.2 45.1 54.4 101.17 * * *

8 48.2 0.20 0.22 5.0 47.6 52.7 101.17 * * *

9 47.9 0.22 0.24 19.3 33.5 52.9 101.09 50 - -

10 48.5 0.56 0.58 8.8 43.0 51.9 101.03 51 - -

11 48.6 0.56 0.58 13.3 38.3 51.7 100.93 46 - -

12 49.2 0.42 0.44 28.0 22.9 51.0 100.69 67 - -

13 49.2 0.17 0.19 3.4 48.3 51.8 101.24 * * -

14 50.0 0.10 0.12 7.0 43.0 50.1 100.27 56 - -

15 50.7 0.10 0.12 15.7 33.7 49.5 100.37 60 - -

16 51.1 0.45 0.47 29.8 19.0 48.9 100.52 65 - -

17 51.2 0.33 0.35 39.7 9.0 48.8 100.40 51 2.0/2.59 F

18 53.2 0.64 0.66 2.8 44.3 47.2 101.11 56 - F

19 53.4 0.28 0.30 45.6 0.1 45.8 99.55 77 2.0/1.97 F

Not Fiberizable ** P = Pass F Failed

EXPERIMENTAL DATA

COMPOSITION, WT% 5 Hour

Acidic Amphoteric Saline E-119 Fire Test Oxides Oxides Basic Oxides Total Extraction Thickness 2 Hour NO. SiO₂ Al₂O₃ Total CaO MgO Total Analytical ppm. Si Density Test**

0 to 1 1/2% Amphoteric Oxides

20 53.8 0.33 0.35 35.1 10.8 46.0 100.20 83 2.0/1.9 97 F 21 53.9 0.40 0.42 25.5 20.5 46.1 100.47 68 - - 22 54.5 1.00 1.02 7.5 36.5 44.1 99.67 30 - -

23 55.9 0.08 0.10 43.0 0.45 43.55 99.60 51 2.0/1.94 F

24 56.0 0.40 0.42 27.0 17.0 44.1 100.57 69 2.0/2.12 F

25 56.35 0.20 0.24 34.4 8.25 42.75 99.39 70 2.0/1.87 F

26 56.4 0.91 0.93 35.1 7.39 42.59 99.97 47 - -

27 57.0 1.03 1.05 24.5 17.6 42.2 100.30 46 - -

28 57.0 1.09 1.11 35.0 6.84 41.94 100.10 40 - -

29 57.25 0.92 0.94 36.95 3.95 41.1 99.56 56 1.88/2.20 F

30 57.8 0.75 0.78 34.75 6.2 41.05 99.85 - 2.0 /1.97 F

31 58.1 0.03 0.05 36.7 4.53 41.33 99.53 59 2.0 /1.91 F

32 58.2 1.08 1.10 35.7 4.79 40.59 99.94 80 2.0 /1.91 F

33 58.3 0.03 0.05 40.8 0.31 41.21 99.61 49 2.0 /1.91 F

34 58.4 0.37 0.39 15.3 26.3 41.7 100.54 61 2.0 /1.91 F

35 58.6 0.09 0.11 35.0 5.36 40.46 99.22 74 2.0 /1.94 P

36 58.7 0.05 0.07 40.2 0.27 40.57 99.39 58 2.0 /1.91 F

37 58.5 0.49 0.53 34.4 5.6 40.1 99.32 59 2.0 /2.01 P

38 58.8 0.41 0.43 35.4 6.2 41.7 100.98 56

* = Not Fiberizable ** P = Poor, F = Failed

EXPERIMENTAL DATA

COMPOSITION, WT% 5 Hour

Acidic Amphoteric Saline E-119 Fire Test Oxides Oxides Basic Oxides Total Extraction Thickness 2 Hour

NO. SiO₂ Al₂O₃ Total CaO MqO Total Analytical ppm. Si Density Test**

0 to 1 1/2% Amphoteric Oxides

39 58.9 0.08 0.10 34.2 6.10 40.4 99.45 67 2.0/1.86 P

40 59.0 0.24 0.26 35.9 3.8 39.9 99.21 49 2.0/1.97 P

41 59.1 0.09 0.11 40.3 0.43 40.83 100.09 68 2.0/1.90 P

42 59.2 0.24 0.26 4.7 36.8 41.60 101.11 47 2.5/1.4 F

43 59.15 0.32 0.34 35.55 4.75 40.40 99.94 60 2.0/1.95 P

44 59.4 0.04 0.06 29.8 10.7 40.60 100.11 61 2.0/1.92 P

45 59.5 0.02 0.04 34.2 5.98 40.28 99.87 77 2.0/1.90 P

46 59.5 0.02 0.04 32.1 8.16 40.36 99.95 73 2.0/1.89 F

47 59.6 1.43 1.45 22.5 16.8 39.6 100.8 51 2.0/1.88 F

48 59.6 0.03 0.05 28.7 11.4 40.2 99.9 70 2.0/1.91 P

50 59.8 0.28 0.30 40.5 0.11 40.71 100.86 30 2.0/2.01 P

51 59.9 1.48 1.50 25.8 12.9 39.0 100.55 47 2.0/1.98 P

52 59.9 1.31 1.33 28.1 11.0 39.4 100.78 45 2.0/1.95 P

53 60.0 1.41 1.43 22.3 16.4 39.0 100.58 41 2.0/1.91 P

54 60.3 0.17 0.19 32.3 6.36 38.76 99.30 59 2.0/1.89 P

55 60.4 1.05 1.07 28.5 9.85 38.45 99.97 45 2.0/1.95 P

56 60.5 1.11 1.13 27.9 10.7 38.9 100.68 36 2.0/1.94 F

57 60.7 0.93 0.95 28.7 9.47 38.27 99.97 51 2.0/1.93 P

58 60.8 0.2 0.22 36. 3. 39.10 100.17 56 - -

* = Not Fiberizable ** P = Poor, F = Failed

EXPERIMENTAL DATA

COMPOSITION, WT% 5 Hour

0 to 1 1/2% Amphoteric Oxides

59 61.7 0.02 0.04 32.6 5.19 37.89 99.68 65 2.0/1.97 P

60 62.4 0.04 0.06 21.7 15.5 37.3 99.81 76 2.0/1.88 P

61 62.5 0.02 0.04 30.3 6.64 37.04 99.63 66 2.0/1.92 P

62 62.5 0.03 0.05 29.5 7.70 37.30 99.90 64 2.0/1.82 P

63 63.1 0.02 0.04 31.1 5.28 36.48 99.67 46 2.0/1.95 P

64 63.1 1.25 1.27 25.2 10.2 35.5 99.92 19 2.0/1.96 P65 63.5 1.49 1.51 24.0 10.9 35.0 100.06 12 2.0/1.91 P 66 63.8 1.13 1.15 28.4 5.79 34.29 99.29 52 2.0/2.01 P

63.8 67 1.41 1.43 22.8 11.8 34.7 99.98 17 2.0/1.88 P68 64.1 1.23 1.25 30.97 2.60 33.67 99.07 7 2.0/1.88 P69 64.1 1.47 1.49 28.6 4.83 33.53 99.17 49 2.0/1.99 P 70 65.3 0.03 0.05 27.4 6.68 34.18 99.58 37 2.0/1.91 P71 65.4 1.15 1.17 3.12 30.1 33.32 99.94 46 2.0/1.88 F

72 65.6 0.01 0.03 27.4 6.50 34.0 99.68 35 2.0/2.00 P 73 65.8 0.02 0.04 28.6 5.21 33.91 99.80 44 - - 74 65.9 0.03 0.05 21.9 11.8 33.8 99.80 30 2.0/1.87 P 75 65.9 0.03 0.05 25.8 7.88 33.78 99.78 25 2.0/1.91 P 76 65.4 1.15 1.17 3.12 30.1 33.23 99.84 46 2.0/1.88 F

* = Not Fiberizable ** P = Poor, F = Failed

EXPERIMENTAL DATA

COMPOSITION. WT% 5 Hour

Acidic Amphoteric Saline E-119 Fire Test

Oxides Oxides Basic Oxides Total Extraction Thickness 2 Hour

NO. SiO₂ Al₂O₃ Total CaO MgO Total Analytical ppm. Si Density Test** 1 1/ 2% to 3% Amphoteric Oxides (Cont.)

95 60.2 2.21 2.23 32.7 4.9 37.7 100.18 50 2.0/2.04 P

96 61.4 2.17 2.19 26.2 10.1 36.4 100.04 18 2.0/1.87 P

97 61.4 1.66 1.68 29.9 6.9 36.9 100.03 61 2.0/1.91 P

98 61.8 2.84 2.86 34.0 0.2 34.3 99.01 51 2.0/1.93 P

99 62.0 2.81 2.83 34.1 0.2 34.4 99.28 55 2.0/1.90 P

100 62.1 2.75 2.77 33.8 0.2 34.1 99.02 13 2.0/1.91 P

101 62.7 1.79 1.81 25.6 9.4 35.1 99.66 18 2.0/1.96 P 102 63.0 2.54 2.56 33.1 0.2 33.4 99.05 37 2.0/1.87 P

103 63.9 1.84 1.86 30.7 2.5 33.3 99.11 38 2.0/1.94 P

104 64.1 1.83 1.85 17.7 16.3 34.3 100.4 12 2.0/1.95 P

105 65.1 2.15 2.17 9.74 23.1 33.15 100.57 17 - P

106 65.6 1.56 1.58 2.7 29.7 32.5 99.73 33 2.0/1.91 P

107 66.7 1.80 1.82 30.7 0.1 30.9 99.47 2 2.0/1.90 P

3 to 4% Amphoteric Oxides

108 49.8 3.5 3.52 4.98 40.9 46.18 99.65 33 - -

109 50.3 3.58 3.60 45.0 0.64 45.74 99.69 19 2.0/1.96 F

110 55.1 3.77 3.79 7.89 33.7 41.89 100.93 33 2.0/2.06 P

* = Not Fiberizable ** P = Pass , F = Failed

- EXPERIMENTAL DATA

COMPOSITION. WT% 5 Hour

Acidic Amphoteric Saline E-119 Fire Test

Oxides Oxides Basic Oxides Total Extraction Thickness 2 Hour

NO. SiO₂ Al₂O₃ Total CaO MgO Total Analytical ppm. Si Density Test** 3% to 4% Amphoteric Oxides (Cont.)

111 55.6 0.24 3.66 37.1 4.65 41.85 101.16 - 2.0/2.12 F

112 56.5 0.35 3.65 36.51 4.17 40.78 100.98 - 2.0/1.99 F

113 56.7 3.52 3.54 23.5 16.2 39.8 100.09 19 2.0/1.89 F

114 56.7 3.06 3.08 23.4 16.6 40.28 100.11 40 2.0/4.02 F

115 56.88 0.32 3.64 36.45 4.00 40.45 101.02 51 - -

115a 57.5 3.29 3.31 37.7 0.75 38.55 99.41 6 2.0/1.93 F

116 58.1 3.05 3.07 25.6 12.8 38.5 99.72 20 2.0/1.9 F

117 58.2 3.75 3.77 36.4 0.67 37.17 99.19 38 2.0/2.0 F

119 58.80 3.76 3.78 36.7 0.24 37.04 99.67 28 2.0/1.97 F

120 61.2 3.77 3.79 34.0 0.24 34.34 99.38 18 2.0/1.94 P

4 to 6% Amphoteric Oxides

121 49.7 4.04 4.06 26.4 19.6 46.1 99.91 37 - -

122 55.8 5.20 5.22 30.1 9.2 39.4 100.47 7 2.0/1.88 F

123 56.85 5.40 5.41 31.8 5.65 37.55 99.91 4 2.0/1.99 F

124 57.0 4.68 4.70 22.0 15.6 37.7 99.45 32 2.0/2.00 F

Not Fiberizable ** P = Pass, F = Failed

EXPERIMENTAL DATA

COMPOSITION. WT% 5 Hour

6 to 8% Amphoteric Oxides

125 39.2 6.90 6.92 38.5 14.0 52.6 98.72 37 - - 126 46.9 7.66 7.68 44.8 0.3 45.2 99.83 6 2.0/1.97 F 127 49.3 6.40 6.42 25.3 18.4 43.8 99.57 19 2.0/2.0 F 128 50.4 7.45 7.48 26.2 15.2 41.5 99.43 18 2.0/3.17 F 129 54.7 7.60 7.62 30.7 6.5 37.3 99.67 7 2.0/1.98 F 130 56.1 6.34 6.36 30.6 6.9 37.6 100.11 4 2.0/2.04 F 131 57.9 6.7 6.72 5.9 29.7 35.6 100.27 2 - - 132 58.5 6.16 6.18 31.2 4.0 35.2 99.93 2 2.0/2.01 F 133 59.7 7.08 7.10 27.9 5.1 33.1 99.9 2 2.0/2.04 F

8 to 10% Amphoteric Oxides

134 38.6 9.3 9.32 38.4 13.7 52.2 100.17 12 - - 135 42.8 8.8 9.13 36.7 9.6 46.76 98.69 13 - - 136 44.5 8.76 8.78 45.5 0.52 46.12 99.45 3 - - 137 52.1 8.9 8.92 23.7 16.2 40.0 101.02 1.2 - - 138 52.5 9.67 9.69 33.5 4.21 37.81 100.05 1.0 2.0/1.99 F 139 53.7 8.7 8..72 22.5 16.3 38.9 101.37 1.7 - - 140 56.6 9.2 9.22 23.5 10.9 34.5 100.37 1.2 2.0/2.05 F

* = Not Fiberizable ** P = Pass, F = Failed

EXPERIMENTAL DATA

COMPOSITION, WT% 5 Hour

NO. SiO₂ Al₂O₃ Total CaO MgO Total Analytical ppm. Si Density Test**

10 t :o 12% Amphoteric Oxides

141 41.0 10.05 10.07 48.25 0.3 48.70 99.87 6 2.0/2.00 F

142 51.3 10.9 10.92 37.2 0.2 37.5 99.77 0.8 2.0/2.04 F

143 52.4 10.7 10.72 23.1 16.1 39.3 102.42 0.7 2.0/2.00 F

144 52.7 10.2 10.22 22.1 16.0 38.2 101.12 0.5 - - 12 to 20% Amphoteric Oxides 145 41.5 13.0 13.02 44.2 0.5 44.8 99.37 1.2 - -146 49.8 18.0 18.02 31.5 0.2 32.02 99.89 0.5 - - 147 55.6 12.9 12.92 13.2 18.4 31.7 100.27 1.8 2.0/2.54 F

20 to 30% Amphoteric Oxides 148 36.5 28.4 28.42 34.4 0.3 34.8 99.77 0.6 - -

149 40.3 21.5 21.52 37.5 0.3 37.9 99.77 0.8 - -

150 42.6 25.7 25.72 31.2 0.3 31.6 99.97 0.6 - -

151 48.4 22.4 22.42 16.5 12.6 29.2 100.07 0.5 2.0/2.01 F

152 59.9 22.8 22.82 3.1 14.0 17.2 99.97 0.7 2.0/2.01 F

30 to 40% Amphoteric Oxides

153 45 . 9 31. 3 31. 32 5 . 9 16 . 7 22 . 7 99 . 97 2 . 3 - -

* = Not Fiberizable ** P = Pass, F = Failed

TABLE 5 FIBERS MADE WITH VARIOUS ADDITIVE CONSTITUENTS ANALYSES 5 Hour

Saline E-119 Fire Test

Acidic Amphoteric Basic % Additive Extraction Thickness 2 Hour NO. Oxides Oxides Oxides Misc. Total (Incl. Total) ppm. Si Density Test

Fibers with B₂O₃ Additions

164 65.12 0.06 35.3 100.48 0.32% B₂O₃ 53 2.0/1.94 P

165 64.42 1.20 34.8 100.42 0.52% " 20 2.0/1.88 P 166 65.24 0.06 35.2 100.5 0.64% " 43 2.0/1.89 P 167 65.32 0.06 35.2 100.58 0.82% " 45 2.0/2.00 P 168 65.43 0.06 34.9 100.39 1.33% " 47 2.0/1.95 P

169 65.47 0.06 34.9 100.43 1.37% " 45 2.0/ - P

170 65.82 0.06 34.6 100.48 2.22% " 46 2.0/2.02 P

171 68.01 0.06 32.0 100.07 8.41% " 52 2.0/6.45 P

Fibers with P₂O₅ addition

172 55.65 0.48 43.58 0.02 99.7 6.06% P₂O₅ 71 2.0/1.94 F

Fibers with TiO₂ addition

173 48.6 51.4 - - 100. 10% Tio₂ 0.4 2.01/1.94 P

ANALYSES 5 Hour Saline E-119 Fire Test

Fibers with ZrO₂ additions

174 63.5 1.10 35.92 - 100.52 0.21% ZrO₂ 25 2.0/2.01 P

175 59.2 0.73 39.51 - 99.44 0.40% " 48 2.0/2.00 P

176 59.5 0.73 39.52 - 99.75 0.42% " 55 - -

177 59.7 0.84 39.16 - 99.70 0.50% " 32 - -

178 60.0 0.90 38.78 - 99.68 0.54% " 40 - -

179 59.2 0.93 37.98 - 98.11 0.58% " 46 2.0/2.02 P

180 54.3 1.88 43.12 .01 99.31 0.58% " 67 2.0/2.00 F

181 59.2 1.15 37.73 - 98.08 0.83% " 57 2.0/2.03 P

182 46.85 2.89 49.98 .02 99.74 0.84% " 44 2.0/2.17 F

182a 59.4 2.69 36.96 .02 99.05 2.31% " 25 2.0/2.00 P

183 59.05 2.95 38.07 - 100.09 2.65% " 38 2.0/2.20 P

184 57.96 3.53 38.72 - 100.21 3.11% " 25 2.0/2.37 F

185 57.80 3.68 38.14 - 99.62 3.12% " 10 2.0/2.03 F

186 59.05 3.65 39.51 - 102.21 3.27% " 15 2.1/2.11 P

187 56.88 3.62 40.45 - 100.95 3.30% " 51 - -

188 57.7 3.50 39.0 - 100.20 3.30% " 13 2.0/2.06 P

189 58.19 3.75 38.65 - 100.59 3.36% " 12 - -

190 57.86 3.73 38.88 - 100.47 3.37% " - 2.0/2.00 F

191 58.6 4.25 36.22 - 99.07 3.67% " 7 2.0/2.00 P

192 58.4 4.34 35.79 - 98.53 3.69% " 3 2.0/2.00 P 193 58.65 7.87 35.36 .01 99.89 4.50% " 1.3 2.0/2.00 P

ANALYSES 5 Hour Saline E-119 Fire Test

Test Acidic Amphoteric Basic % Additive Extraction Thickness 2 Hour No. Oxides Oxides Oxides Misc. Total (Incl.Total) ppm. Si Density Test

Fibers with FeO₃ additions

194 64.9 0.06 35.38 - 100.34 0.06% FeO₃ & MnO 56 2.01/1.88

195 49.8 18.02 31.92 0.07 99,81 0.22% " " 0.5 -

196 50.4 7.49 42.04 0.07 100.00 0.52% " " 18

197 64.34 0.06 34.7 - 99.1 0.50% " " 51 2.0/1.91 P

198 63.70 1.20 33.02 - 98.62 0.69% " " 24 2.0/1.88 F

199 63.54 1.20 33.46 - 98.20 0.72% " " 35 2.0/2.00 P

200 38.9 6.72 54.40 0.07 100.09 0.80% " " 17

201 64.3 0.06 35.96 - 100.32 0.96% " " 45 2.0/1.88 P

202 44.6 0.94 51.92 - 97.46 1.02% " " 49

203 63.3 1.15 34.99 - 99.44 1.61% " " 12 2.0/1.95 F

204 63.6 0.06 36.62 - 100.15 1.92% " " 31 2.0/1.91 P

205 43.8 15.28 40.94 0.13 100.02 2.94% " " 1. 3

206 62.3 1.20 36.05 - 99.55 3.05% " " 7 2.0/1.98 F

207 63.3 0.06 36.95 - 100.31 3.45% " " 18 2.0/1.88 F

208 43.9 14.32 41.6 - 99.82 3.50% " " 2

209 62.0 0.06 38.31 - 100.37 4.81% " " 13 2.0/1.98 F

210 60.0 2.0 38.0 - 100.0 8.0% " " 0. 9 2.0/2.00 F

211 60.0 - 40.0 - 100.0 20.0% " " 0. 7 2.0/2.00 F

ANALYSES 5 Hour Saline E-119 Fire Test

Fibers with La₂O₃ additions

212 58.1 0.06 41.47 99.63 0.00% La₂O₃ 76 2.0/1.97 F

213 57.8 0.06 41.82 99.68 0.56% " 69 2.0/1.97 F

214 57.5 0.06 41.72 99.28 0.72% " 78 2.0/1.98 F

215 56.9 0.06 41.58 99.54 0.92% " 70 2.0/1.98 F

Fibers with Cr₂O₃ additions

216 62.6 0.51 36.61 99.72 0.09% Cr₂O₃ 28 2.0/2.16 P

Fibers with Na₂O additions

217 64.7 0.06 35.58 100.34 0.28% Na₂O 45 2.0/1.91 P

218 64.5 0.06 35.68 100.21 0.45% " 57 2.0/1.97 P

219 64.4 0.06 35.80 100.26 0.71% " 54 2.0/1.97 P

220 63.5 1.20 35.70 100.40 0.87% " 30 2.0/1.90 P

221 64.3 0.06 35.63 99.99 0.93% " 51 2.0/1.90 P

222 64.2 0.06 36.11 100.37 1.11% " 57 2.0/1.99 P

223 64.0 0.06 36.3 100.36 1.40% " 43 2.0/1.99 P

224 63.0 0.06 37.0 100.06 2.60% " 50 2.0/2.16 F

225 60.3 0.06 39.74 100.1 6.84% " 70 2.0/1.87 F

ANALYSES 5 Hour

Saline E-119 Fire Test

Test Acidic Amphoteric Basic % Additive Extraction Thickness 2 Hour No. Oxides Oxides Oxides Misc. Total (Incl. Total) ppm. Si Density Test

Conventional Mineral Wool Fibers

226 40.0 9.50 49.97 0.69 100.16 - 7 2.0/3.50 F

227 39.92 13.99 45.82 0.74 100.47 - 1.2 2.0/5.23 F

228 38.49 12.24 49.35 0.61 100.69 - 0.6 2.0/3.42 F

229 41.87 17.10 41.53 0.64 101.14 - 1.0 2.0/3.86 F

Refractory Fibers - (Fibers with less than 25% Basic Oxides) 231 31.0 47.52 21.4 - 99.92 - 2 2.0/2.10 F 232 37.1 59.2 3.3 - 99.6 - 0.6 2.0/5.38 F 233 50.0 40.0 10.0 - 100 - 0.8 2.0/2.00 P234 54.0 46.0 - - 100 - 0.3 2.0/2.00 P 235 59.62 25.55 14.23 0.7 100.11 - 0.3 2.0/2.00 P236 52.1 46.39 1.13 - 99.62 - 1.0 - - 237 52.0 46.84 1.07 - 99.91 - 0.4 - -

238 49.8 49.22 1.02 - 100.04 - 0.3 - -

239 48.6 50.05 1.00 - 99.65 - 0.4 - -

240 47.8 51.00 0.98 - 99.78 - 0.3 - -

241 46.2 53.10 0.93 - 100 . 23 - 0.4 - -

242 28 72 - - 100 - 0.5 - -

243 64.5 27.4 8.4 - 100. 3 - 0.8 2.0/1.85 F

TABLE 6

CONTINUOUS SERVICE TEMPERATURE

FOR CONSTANT SiO₂/CaO/MgO RATIOS

0 5 10 20 30

SiO₂/CaO/MgO Ratio Continuous Service Temperature for max 5% shrinkage

°F 50/50/0 1480 1480 1470 1420 1550

50/40/10 1440 1430 1420 1400 1520

50/30/10 1400 1380 1370 1350 1480 60/40/0 1500 1460 1460 1460 1600 60/30/10 1430 1420 1400 1410 1520 60/20/20 1380 1370 1360 1350 1500

Reasonable modifications and variations are possible from the foregoing disclosure without departing from either the spirit or scope of the invention as defined in the claims.

FOR THE PURPOSES OF INFORMATION ONLY

Codes used to identify States party to the PCT on the front pages of pamphlets publishing international applications under the PCT.

AT Austria ES Spain MG Madagascar

AU Australia Fi Finland ML Mali

BB Barbados FR France MR Mauritania

BE Belgkπn GA Gabon MW Malawi

BF Burkina Fasso GB United Kingdom NL Netherlands

BG Bulgaria HU Hungary NO Norway

BJ Benin rr Italy RO Romania

BR Brazil JP Japan SD Sudan

CA Canada KP Democratic People's Republic SE Sweden

CF Central African Republic of Korea SN Senegal

CG Congo . KR Republic of Korea SU Soviet Union

CH Switzerland U Liechtenstein TD Chad

CM Cameroon LK Sri Lanka TG Togo

DE Germany. Federal Republic of LU Luxembourg US United States of America

DK Denmark MC Monaco

PCT WORLD INTELLECTUAL PROPERTY ORGANIZATION International Bureau

INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

(51) International Patent Classification 4 (11) International Publication Number: WO 89/120 C03C 13/00, 13/02, 25/06

A3 (43) International Publication Date: 14 December 1989 (14.12.

(21) International Application Number: PCT/US89/02288 (81) Designated States: AT (European patent), AU, BE (Eu pean patent), BR, CH (European patent), DE (Europ

(22) International Filing Date : 25 May 1989 (25.05.89) patent), DK, FI, FR (European patent), GB (Europ patent), IT (European patent), JP, KP, KR, LU (Eu pean patent), NL (European patent), NO, SE (Europ

(30) Priority data: patent).

201,513 1 June 1988 (01.06.88) US

Published

(71) Applicant: MANVILLE SALES CORPORATION [US/ With international search report.

US]; Manville Plaza, 5th Floor, P.O. Box 5108, Denver, Before the expiration of the time limit for amending t CO 80217 (US). claims and to be republished in the event of the receipt amendments.

(72) Inventors: OLDS, Leonard, Elmo ; 977 South Lake Gulch

Road, Castle Rock, CO 80104 (US). KIELMEYER, Wil(88) Date of publication of the international search report: liam, Henry ; 3374 West Chenango Avenue, Englewood, 5 April 1990 (05.04.9 CO 80110 (US).

(74) Agent: SCHRAMM, William, J.; Brooks & Kushman, 2000 Town Center, Suite 2000, Southfϊeld, MI 48075 (US).

(54) Title: PROCESS FOR DECOMPOSING AN INORGANIC FIBER

(57) Abstract

Inorganic fibers which have a silicon extraction of greater than 0.02 wt% Si/day in physiological saline solutions. The fib contains Si0₂, MgO, CaO, and at least one of A1₂0₃, Zr0₂, Ti0 , B₂0₃, iron oxides, or mixtures thereof. Also disclosed a inorganic fibers which have diameters of less than 3.5 microns and which pass the ASTM E-l 19 two hour fire test when pr cessed into a fiber blanket having a bulk density in the range of about 1.5 to 3 pcf.

FOR THEPURPOSESOFINFORMATIONONLY

Codes used to identify States party to the PCT on the front pages ofpamphlets publishing international applications under the PCT.

AT Austria FI Finland ML Mali

AU Australia FR France MR Mauritania

BB Barbados GA Gabon MW Malawi

BE Belgium GB United Kingdom NL Netherlands

BF Burkina Fasso Hll Hungary NO Norway

BG Bulgaria rr Italy RO Romania

BJ Benin JP Japan SD Sudan

BR Brazil KP Democratic People's Republic SE Sweden

CF Central African Republic ofKorea SN Senegal

CG Congo KR RepublicofKorea SU Soviet Union

CH Switzerland u Liechtenstein TD Chad

CM Cameroon LK Sri Lanka TG Togo

DE Germany. Federal Republicof LU Luxembourg US United States of America

DK Denmark MC Monaco

ES Spain MG Madagascar

Claims

1. A process for decomposing a silicacontaining fiber comprising the steps of:

1. providing an inorganic fiber prepared from a composition consisting essentially of:

(a) 0.06-10 wt% of a material selected from the group consisting of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof;

(b) 35-70 wt% SiO₂;

(c) 0-50 wt% MgO; and

(d) the remainder consisting essentially of CaO, the total being 100% by weight;

2. subjecting the silica-containing fiber to a physiological saline fluid; and

3. extracting the silica at a rate of at least 5 parts per million (ppm) of silicon in 5 hours, thereby decomposing the silicacontaining fiber.

2. The process of Claim 1 wherein the composition of subsection 1(a) ranges from 0.06-5 wt% of material selected from the group consisting of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof.

3. The process of Claim 1 wherein the composition of subsection 1(c) ranges from 0.25-50 wt% MgO.

4. The process of Claim 1 wherein the composition consists essentially of: (a) 0.06-1.5 wt% of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof;

(b) 40-70 wt% SiO₂; (c) 0-50 wt% MgO; and

(d) the remainder consisting essentially of CaO, the total being 100% by weight.

5. The process of Claim 4 wherein the composition in subsection 1(c) ranges from 0.25-50 wt%

MgO.

6. The process of Claim 1 wherein the composition consists essentially of:

(a) 1.5-3 wt% of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof;

(b) 40-66 wt% SiO₂;

(c) 0-50 wt% MgO; and

7. The process of Claim 1 wherein the composition of subsection 1(c) ranges from 0.25-50 wt% MgO.

8. The process of Claim 1 wherein the composition consists essentially of:

(a) 3-4 wt% of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof;

(b) 40-63 wt% SiO₂;

(c) 0-50 wt% MgO; and (d) the remainder consisting essentially of CaO, the total being 100% by weight.

9. The process of Claim 8 wherein the composition of subsection 1(c) ranges from 0.25-50 wt%

MgO.

10. The process of Claim 1 wherein the composition consists essentially of:

(a) 4-6 wt% of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof;

(b) 40-60 wt% SiO₂;

(c) 0-25 wt% MgO; and

11. The process of Claim 10 wherein the composition of subsection 1(c) ranges from 0.25-25 wt% MgO.

12. The process of Claim 1 wherein the composition consists essentially of:

(a) 6-8 wt% of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof;

(b) 35-54 wt% SiO₂;

(c) 0-25 wt% MgO; and (d) the remainder consisting essentially of CaO, the total being 100% by weight.

13. The process of Claim 12 wherein the composition of subsection 1(c) ranges from 0.25-25 wt% MgO.

14. The process of Claim 1 wherein the composition consists essentially of:

(a) 8-10 wt% of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof; (b) 35-54 wt% SiO₂;

(c) 0-20 wt% MgO; and

15. The process of Claim 14 wherein the composition of subsection 1(c) ranges from 0.25-20 wt% MgO.

16. The process of Claim 1 wherein the fiber has a diameter of less than 3.5 microns.

17. The process of Claim 1 wherein the silicon extraction rate is at least 20 ppm, the Al₂O₃ content is about 0.06-7 wt%, and the SiO₂ content is about 40-66 wt%.

18. The process of Claim 1 wherein the silicon extraction rate is at least about 50 ppm, the Al₂O₃ content is about 0.06-3 wt%, and the SiO₂ content is about 40-60 wt%.

19. The process of Claim 1 wherein the silicon extraction rate is at least about 50 ppm, the Al₂O₃ content is about 0.06-0.75 wt%, and the SiO₂ content is about 40-60 wt%.

20. A process of protecting a structural wall from fire comprising the steps of:

1. providing a fiber blanket having a bulk density in the range of about 1.5 to about 3 lbs. per cubic foot (pcf); wherein the fiber blanket has the ability to pass ASTM E-119 two-hour fire test; the fibers in the blanket have a diameter less than about 3.5 microns; and the fiber is an inorganic fiber prepared from a composition consisting essentially of: (a) 0-7 wt% of Al₂O₃, ZrO₂, TiO₂,

B₂O₃, iron oxides and mixtures thereof;

(b) 58-70 wt% SiO₂

(c) 0-21 wt% MgO ;

(d) 0-2 wt% alkali metal oxide; and (e) the remainder consisting essentially of CaO, the total being 100% by weight; and

2. placing the blanket next to the wall, and thereby protecting the wall from fire.

21. The process of Claim 20 wherein the composition of subsection 1(a) ranges from 0.06-7 wt% of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof.

22. The process of Claim 20 wherein the composition of subsection 1(c) ranges from 0.25-21 wt%

MgO.

23. The process of Claim 20 wherein the composition consists essentially of:

(a) 0.06-3.0 wt% of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof;

(b) 58.5-70 wt% SiO₂; (c) 0-21 wt% MgO;

(d) 0-2 wt% alkali metal oxide; and

(e) the remainder consisting essentially of Cao, the total being 100% by weight.

24. The process of Claim 20 wherein the composition of subsection 1(c) ranges from 0.25-21 wt% MgO.

25. The process of Claim 20 wherein the composition consists essentially of:

(a) from about 3 wt% up to and including 4 wt% of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof;

(b) 58-63 wt% SiO₂; (c) 0-8 wt% MgO;

(d) 0-2 wt% alkali metal oxide; and

26. The process of Claim 25 wherein the composition in subsection 1(c) ranges from 0.25-8 wt% MgO.

27. The process of Claim 25 wherein the composition consists essentially of: (a) from about 4 wt% up to and including 6 wt% of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof;

(b) 58-61 wt% SiO₂;

(c) 0-7 wt% MgO; (d) 0-2 wt% alkali metal oxide; and (e) the remainder consisting essentially of Cao, the total being 100% by weight.

28. The process of Claim 25 wherein the composition of subsection 1(c) ranges from 0.25-7 wt%

MgO.

29. An inorganic fiber having an average fiber diameter of less than about 3.5 microns, a silicon extraction rate greater than about 0.02 wt% Si/day in a physiological saline solution and having a composition consisting essentially of about:

(a) 0.06-5.0 wt% of material selected from the group consisting of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof;

(b) 35-70 wt% SiO₂;

(c) 0-50 wt% MgO; and

(d) the remainder consisting essentially of Cao, the total being 100 wt%.

30. An inorganic fiber having a silicon extraction of at least about 10 ppm over a 5 hour period in physiological saline solution and having a composition consisting essentially of about:

(a) 0.06-1.5 wt% of material selected from the group consisting of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof;

(b) 40-70 wt% SiO₂;

(c) 0-50 wt% MgO; and (d) the remainder consisting essentially of CaO, the total being 100 wt%.

31. An inorganic fiber according to Claim 30 having a silicon extraction of at least about 20 ppm, an average fiber diameter of less than about 3.5 microns, and having an SiO₂ content of about 40-66 wt%.

32. An inorganic fiber according to Claim 30 having a silicon extraction of at least about 50 ppm and having an SiO₂ content of about 40-60 wt% and a MgO content of about 0.25-25 wt%.

33. An inorganic fiber having a silicon extraction of at least about 10 ppm over a 5 hour period in physiological saline solutions and having a composition consisting essentially of about:

(a) 1.5-3 wt% of material selected from the group consisting of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof;

(b) 40-66 wt% SiO₂;

(c) 0-50 wt% MgO; and

(d) the remainder consisting essentially of CaO, the total being 100 wt%.

34. An inorganic fiber according to Claim 33 having a silicon extraction of at least about 20 ppm, an average fiber diameter of less than about 3.5 microns, and an MgO content of from about .25-50 wt%.

35. An inorganic fiber according to Claim 33 having a silicon extraction of at least about 50 ppm, an SiO₂ content of from about 40-54 wt%, and an MgO content of from about 0.25-18 wt%.

36. An inorganic fiber having a silicon extraction of at least about 10 ppm over a 5 hour period in physiological saline solutions and having a composition consisting essentially of about:

(a) 3-4 wt% of material selected from the group consisting of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof;

(b) 40-63 wt% SiO₂;

(c) 0-50 wt% MgO; and

(d) the remainder consisting essentially of CaO, the total being 100 wt%.

37. An inorganic fiber according to Claim 36 having a silicon extraction of at least about 20 ppm, an average fiber diameter of less than about 3.5 microns, and a SiO₂ content from about 40-58 wt%.

38. An inorganic fiber according to Claim 37 having a silicon extraction of at least about 50 ppm and an SiO₂ content of from about 40-52 wt% and a MgO content of from about .25-18 wt%.

39. An inorganic fiber having a silicon extraction of at least about 10 ppm over a 5 hour time period in a physiological saline solution and having a composition consisting essentially of about:

(a) 4-6 wt% of material selected from the group consisting of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof;

(b) 40-59 wt% SiO₂;

(c) 0-46 wt% MgO; and

(d) the remainder consisting essentially of CaO, the total being 100 wt%.

40. An inorganic fiber according to Claim 39 having a silicon extraction of at least about 20 ppm, an average fiber diameter of less than about 3.5 microns, and an SiO₂ content from about 40-58 wt%.

41. An inorganic fiber having a diameter of less than about 3.5 microns and which passes the ASTM E-119 two hour fire test when processed into a fiber blanket having a bulk density in the range of about 1.5 to 3 pcf, said inorganic fiber having a composition consisting essentially of:

(a) .06-7 wt% of material selected from the group consisting of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof; (b) 58-70 wt% SiO₂;

(c) 0-21 wt% MgO;

(d) 0.1-2 wt% alkali metal oxide; and

(e) the remainder consisting essentially of CaO, the total being 100 wt%; wherein the amount of alumina + zirconia is less than 6 wt% and the amount of iron oxides or alumina + iron oxides is less than 2 wt%.

42. An inorganic fiber according to Claim 41 having a composition consisting essentially of about:

(a) .06-1.5 wt% of material selected from the group consisting of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof; and (b) 58.5-70 wt% SiO₂.

43. An inorganic fiber according to Claim 42 having a silicon extraction of at least about 10 ppm over a 5 hour period in physiological saline solutions.

44. An inorganic fiber according to Claim 41 having a composition consisting essentially of about:

(a) greater than 1.5 wt% up to and including 3 wt% of material selected from the group consisting of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof; and

(b) 58.5-66 wt% SiO₂.

45. An inorganic fiber according to Claim 44 having a silicon extraction of at least about 10 ppm over a 5 hour period in a physiological saline solution.

46. An inorganic fiber according to Claim 41 having a composition consisting essentially of about:

(a) greater than 3 wt% up to and including 4 wt% material selected from the group consisting of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof;

(b) 58-63 wt% SiO₂;

(c) .25-8 wt% MgO;

(d) .1-2 wt% alkali metal oxide; and (e) the remainder consisting essentially of CaO, the total being 100 wt%.

47. An inorganic fiber according to Claim 46 having a silicon extraction of at least about 10 ppm over a 5 hour period in physiological saline solutions.

48. An inorganic fiber according to Claim 41 having a composition consisting essentially of about:

(a) greater than 4 wt% up to and including 6 wt% of material selected from the group consisting of Al₂O₃, ZrO₂, TiO₂,

B₂O₃, iron oxides and mixtures thereof;

(b) 58-59 wt% SiO₂;

(c) .25-7 wt% MgO;

(d) .1-2 wt% alkali metal oxide; and

(e) the remainder consisting essentially of CaO, the total being 100 wt%.

49. An inorganic fiber according to Claim 48 having a silicon extraction of at least about 10 ppm over a 5 hour period in physiological saline solutions.

50. An inorganic fiber having a silicon extraction of greater than about 0.02 wt% Si/day in a physiological saline solution, a continuous service temperature above about 1450ºF and having a composition consisting essentially of about:

(a) .06-5 wt% of material selected from the group consisting of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof; (b) 40-70 wt% SiO₂;

(c) 0-6 wt% MgO; and

(d) the remainder comprising essentially of CaO, the total being 100 wt%.

51. The fiber of Claim 50 wherein the composition of subsection (c) has an amount of 0.25-6 wt%

MgO.

52. An inorganic fiber having a silicon extraction of greater than about 0.02 wt% Si/day in a physiological saline solution, having a continuous service temperature above about 1500°F and having a composition consisting essentially of about:

(a) .06-1.5 wt% of material selected from the group consisting of Al₂O₃, ZrO₂, TiO₂, B₂O₃, iron oxides and mixtures thereof; (b) 60-70 wt% SiO₂;

(c) 0-1 wt% MgO; and

(d) the remainder consisting essentially of CaO, the total being 100 wt%.

53. The fiber of Claim 52 wherein the composition of subsection (c) has an amount 0.25-1 wt% MgO.

54. An inorganic fiber according to Claims 1 or 29 made from pure oxidic raw materials.

55. An inorganic fiber according to Claim 1 or 29 or 41 in which at least a portion of the raw materials is selected from a group consisting of talc, metallurgical slags, siliceous rocks, kaolin, and mixtures thereof.

56. An inorganic fiber having a composition consisting essentially of about: (a) 8.0-9.3 wt% Al₂O₃;

(b) 39-52 wt% SiO₂;

(c) 22-38 wt% CaO; and

(d) 7-14 wt% MgO, the total being 100 wt% and having a silica extraction in a saline solution of at least about 5 ppm over a 5 hour period.

57. An inorganic fiber composition having a composition consisting essentially of about:

(a) 49-61 wt% SiO₂;

(b) 10-36 wt% CaO; and (c) 3-23 wt% MgO, the total being

100 wt% and having a SiO₂ extraction in a saline solution of between about 24-67 ppm over a 5 hour period.