Abstract:
The glass compositions of the present invention contain at least 2.0 wt % Al 2  O 3  to give resulting glass fiber an acceptable chemical durability for product performance, but no more than 3.0 wt % to ensure the fiber maintains a relatively high biosolubility. The compositions further include relatively high amount of Na 2  O+K 2  O+MgO+CaO, which tends to increase fiber biosolubility and allows for the use of reduced amounts of B 2  O 3  in the composition. The glass compositions have KI values that generally equal or exceed a KI value of 40 and are suitable for rotary processing. The compositions have liquidus temperatures below about 1800° F. and viscosities above 300 Poise at the liquidus temperature. For higher B 2  O 3  compositions the liquidus temperatures are below 1650° F., and the viscosities are above 1,000 Poises at the liquidus temperatures.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     Not Applicable 
     STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT 
     Not Applicable 
     BACKGROUND OF THE INVENTION 
     The present invention is directed generally to glass compositions, and more particularly to glass fiber compositions having high KI values and structural durability. 
     Glass fiber, or fiberglass, insulation is well known and has been a commercial product for many years. Glass fiber insulation is widely used both residentially and commercially. 
     Generally, the insulation is made from intertwined soda lime alumina borosilicate glass fibers which are held together with a binder. The glass fibers are generally produced using SiO 2  with a number of additives, such as Na 2  O, K 2  O, CaO, MgO, BaO, B 2  O 3 , and Al 2  O 3 , that enhance various properties of fibers. The binder may be any suitable material, but quite commonly is a phenol-formaldehyde resin or a urea formaldehyde resin. 
     A rotary process is often used to form the glass fibers. The rotary process typically involves the introduction of molten glass into a rotating device, called a spinner, which contains a plurality of holes circumferentially distributed around the spinner. The spinner is rotated about an axis to produce a centrifugal force on the molten glass. The rotation of the spinner forces the molten glass through the plurality of holes. 
     An annular stream of hot gases is passed around the spinner to contact and attenuate the fibers passing through the holes. A spray nozzle is positioned to coat the attenuated fibers with the binder. 
     A conveyer collects the binder-coated fibers in the form of a blanket, or batt, and the blanket is heat cured to produce the final insulation. The rotary process can be used to produce insulation having different densities by varying the conveyer speed and the thickness of the cured insulation. 
     Glass fiber insulation has been used to replace, or in lieu of, asbestos fiber insulation in many applications. It is generally believed that asbestos fibers, when inhaled, can result in significant disease in man. Though the exact mechanism responsible for the biological activity of asbestos fibers is unknown, it is widely believed that an important factor in the mechanism is the residence time of the fibers in the lungs. 
     Unlike asbestos fibers, glass fibers have not been linked to disease in man. Glass fiber also appears to have a much shorter residence time in the lungs than asbestos fibers. 
     The residence time of glass fibers in the lungs will depend, at least in part, upon chemical dissolution of the fiber. The rate of chemical dissolution of a material in biological fluid is generally referred to as the biosolubility or biological degradability of the material. 
     Despite the lack of a link between glass fibers and human disease, some countries, for example Germany, have proposed regulations for the use of glass fibers in insulation products. Glass fiber compositions that meet the standard in the proposed regulations are considered to be free of suspicion as a disease causing agent and can be used for both commercial and residential installations. 
     The regulations are based on a desire to minimize the residence time of the glass fiber in the lungs. It is a hope that minimizing the residence time of the glass fiber will decrease the possibility, if any, of subsequent disease. 
     The proposed German regulations for biosolubility require that glass fibers have a numerical index (KI) greater than or equal to 40 to be considered to be free of suspicion. The KI index, which is sometimes referred to as the Wardenbach Index, is described by the equation: 
     
         KI=Σ(Na.sub.2 O, K.sub.2 O, CaO, MgO, BaO, B.sub.2 O.sub.3)-2(Al.sub.2 O.sub.3) 
    
     where the values for each oxide correspond to the weight percentage of that oxide in the glass composition. 
     The index used in the regulation places severe constraints on the compositions of the glass, expressly on the levels of alumina (Al 2  O 3 ) and implicitly on the level of silica (SiO 2 )in the glass composition. Manufacturers must now produce glass fibers which meet the proposed regulations, while maintaining standard performance criteria for the products. The criteria include that the glass fiber must be producible using standard wool processes, have sufficient durability in use, and acceptable insulating properties. 
     Silica is the primary component in glass fiber and provides most of the structural and physical properties of the fiber. Alumina is primarily used in the fiber to provide additional durability to the fiber. 
     Initial attempts to produce glass fiber that complies with the regulations involved using reduced levels of alumina in the glass composition to increase the KI index. However, low alumina glass fibers tend to have poor durabilities. 
     A number of glass composition have been reported as having improved biosolubility or biodegradability. For example, Potter, U.S. Pat. No. 5,055,428, Cohen et al., U.S. Pat. No. 5,108,957, Nyssen, U.S. Pat. No. 5,332,698, and Bauer et al., U.S. Pat. No. 5,401,693, all describe glass fibers having improved biosolubility. Also, published PCT applications WO 95/31411, WO 95/32925, WO 95/32926, WO 95/32927, and WO 95/35265 and numerous published German applications have reported glass compositions having increased biodegradability. 
     Despite the improvements presented in the aforementioned patents and applications, the glasses failed to meet the KI≧40 standard or significant processing and performance problems remain. The decreased performances and increased processing costs for glass compositions designed to meet the new biological standards is a clear shortcoming in the industry. In addition, higher alumina compositions of the prior art provide performance versatility, yet are either not acceptable in the emerging regulated marketplace or suffer from increased processing costs. Accordingly, there is still a need for a glass composition which has increased biosolubilities (KI value≧40), while possessing acceptable processing properties, such as viscosity and liquidus temperatures, as well as acceptable performance and durability in use. 
     BRIEF SUMMARY OF THE INVENTION 
     The above objectives and others are accomplished by glass compositions in accordance with the present invention. The glass compositions contain at least 2.0 wt % Al 2  O 3  to give resulting glass fiber an acceptable chemical durability for product performance, but no more than 3.0 wt % to ensure the fiber maintains a relatively high biosolubility. The compositions further include relatively high amount of Na 2  O+K 2  O+MgO+CaO, which tends to increase fiber biosolubility and allows for the use of reduced amounts of B 2  O 3  in the composition. 
     The glass compositions have KI values that generally equal or exceed a KI value of 40 and are suitable for rotary processing. The compositions have liquidus temperatures below about 1800° F., and have viscosities above 300 Poise at the liquidus temperatures. 
     In one aspect of the invention glasses are formulated with relatively high amounts of B 2  O 3  and low amounts of CaO+MgO. The high B 2  O 3  glasses were found to have very low liquidus temperatures (&lt;1650° F.) and higher viscosities (&gt;1,000 Poise) at the liquidus temperature. 
     In another aspect of the invention, glasses are formulated with relatively low amounts of B 2  O 3  and high amounts of CaO+MgO. The low B 2  O 3  glasses were found to have slightly higher liquidus temperatures but still sufficiently low to be formed into fibers by the rotary process (liquidus temperatures &lt;1800° F., and viscosities at the liquidus temperature &gt;300 Poise). 
     In some situations the low B 2  O 3  /high (CaO+MgO) glasses are highly advantageous. For example, lower amounts of B 2  O 3  can result in significantly lower batch costs. 
     Also, the lower B 2  O 3  level in the composition can result in lower volatile emissions both during melting and forming. When formed by the rotary process, the lower viscosity low B 2  O 3  glasses can be extruded through the spinner holes and attenuated without significant reheating of the fibers. 
     In another aspect of the invention, glasses are formulated with low amounts of MgO, generally below about 3.0 to 3.5 wt % have significantly improved chemical durabilities with respect to water. These compositions provide for an improved product performance in addition to improved biosolubility. 
     In another aspect of the invention, glasses are formulated with higher amounts of MgO, generally between about 2.0 and 6.0 wt %, and preferably between about 3.0 and 5.0 wt %. It was found that these glasses could be formulated with lower amounts of B 2  O 3 , while still maintaining an acceptable liquidus temperature and viscosity at the liquidus temperature. Advantages of these glasses include lower cost and less volatile emissions during melting and forming. 
     The compositions of the present invention provides glass compositions that meet proposed biosolubility standards, while maintaining acceptable performance and durability as glass fiber insulation. Accordingly, the present invention overcomes the aforementioned difficulties of the prior art in meeting both public health standards and commercial requirements. These advantages and others will become apparent from the following detailed description of the invention. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The present invention will be described generally with reference to present preferred embodiments of the invention only for the purpose of providing examples of the invention and not for purposes of limiting the same. 
     The applicants have found that acceptable glass processing and fiber biosolubility and durability can be maintained in glass fiber by providing compositions including alumina in a range of 2-3%, B 2  O 3  in the range of 6-15%, and increased levels of alkali and alkaline oxides over the prior art. Compositions of the present invention provide a balance between increased durability and biosolubility to address the shortcomings of the prior art. 
     The SiO 2  content in compositions of the present invention ranges from 49-54%. The present invention provides for lower levels of silica to provide for increased levels of additives that are used to improve the biosolubility and the durability of the resulting glass fibers. 
     The Al 2  O 3  content in the composition should be approximately 2% or higher to provide sufficient performance durability. However, as the alumina content begins to exceed approximately 3%, the biosolubility of the composition will begin to deteriorate. It is preferable that the alumina content of the composition ranges from 2.1-2.9% and more preferably from 2.1-2.6% to provide a more balanced composition. 
     To compensate for the increased levels of alumina and its detrimental affect on the biosolubility, increased levels of alkali and alkaline oxides are included in the composition. Specifically, higher levels of MgO, CaO, Na 2  O and K 2  O can be used to improve the KI index and to lower the liquidus temperature of the compositions. 
     Na 2  O is included in an amount ranging from approximately 16-22% depending on the desired properties. Na 2  O will generally provide for lower viscosities and better melting characteristics for the glass. Preferably, the amount of Na 2  O ranges from 18-21% and more preferably from 19-21% in the composition. In this range, the amount of B 2  O 3  in the composition can be reduced as further discussed within. 
     K 2  O is included in lower amounts, generally 0-2%, depending upon the amount of Na 2  O included in the composition. K 2  O at low levels tends to enhance the characteristics associated with Na 2  O. For example, somewhat lower liquidus temperatures can be achieved without substantial quantities of B 2  O 3 , if the combined amount of K 2  O and Na 2  O is approximately 20% or higher. 
     MgO is included in the composition ranges from 0-8% to provide for somewhat lower liquidus temperatures and viscosities at a lower cost. When MgO is included in quantities less than approximately 3.5%, the resulting glass fibers have improved durability with respect to water. 
     In addition, when MgO is included in a range of about 2-6%, and more preferably 3-5%, the glass compositions can be formulated with lower B 2  O 3  quantities. When formed by the rotary process, the lower viscosity low B 2  O 3  glasses can be extruded through the spinner holes and attenuated without significant reheating of the fibers. 
     CaO is included in the composition in quantities ranging from 7-14%. The CaO provides for a lower viscosity and improved durability. 
     B 2  O 3  is included in the composition in quantities ranging from 5.5-15%. The B 2  O 3  primarily serves to significantly lower the liquidus temperature and the viscosity of the composition, but also provides durability in resulting fibers. The glass compositions formed with high concentration of B 2  O 3 , e.g. 13%, were found to have very low liquidus temperatures (&lt;1650° F.) and higher viscosities (&gt;1,000 Poise) at the liquidus temperature. 
     While including high concentrations of B 2  O 3  in the glass compositions tends to increase the cost, high B 2  O 3  glasses can be formed into fibers at quite low temperatures and at high viscosities. These forming conditions can greatly increase the spinner life which can compensate for the increased cost of the glass batch. 
     Prior art glass compositions conforming to the KI index regulations generally provide for increased levels of B 2  O 3  to compensate in part for the increased levels of alumina. However, a disadvantage of including increased levels of B 2  O 3  are higher costs associated with B 2  O 3 . Another disadvantage is that B 2  O 3  is volatile and higher concentrations produce higher emissions that must be controlled, which can further lead to increased costs. For these reasons, it is preferred to limit the B 2  O 3  content to 15%. 
     In view of the disadvantages associated with the various constituents included in glass compositions, the present invention attempts to balance the composition to provide for more versatile and better performing glass compositions. 
     The following examples are provided to demonstrate the present invention and not to limit the same. 
    
    
     EXAMPLES 
     A number of compositions were prepared by methods known in the art to provide examples of compositions of the present invention. For each sample, the liquidus temperature of the composition was determined. Also, the temperature at which the viscosity of the glass is approximately 1000 poise was determined. The viscosity at the liquidus temperature (η TL ) is shown for a number of compositions. 
     In addition, durability testing was performed on a number of samples. The durability test consisted of preparing 10 μm diameter continuous fibers from each composition. A 1 g sample of the fiber was placed in 100 ml of water and maintained at a temperature of 96° F. for 24 hours. Following the water exposure, the sample was removed from the water, dried and weighed. The post-test weight of the sample was compared to the pretest weight to calculate the % weight loss during testing. 
     
         ______________________________________Constituent\Sample #          1       2        3______________________________________SiO.sub.2      53.69   53.69    50.72Al.sub.2 O.sub.3          2.0     2.0      3.0B.sub.2 O.sub.3          10.0    8.0      11.9Na.sub.2 O     19.3    19.3     19.3K.sub.2 O      0.7     0.7      0.7MgO            4.35    4.96     3CaO            9.88    11.27    11.3Fe.sub.2 O.sub.3          0.08    0.08     0.08KI Index       40.23   40.23    40.20Liquidus       1618    1707     1664Temperature T.sub.L (° F.)Temp. @ η = 1000 Poise          1632    1643     1600η.sub.TL (Poise)          1,170   540% weight loss  4.12    4.11______________________________________Constituent\Sample #          4       5        6     7______________________________________SiO.sub.2      53.42   53.42    53.42 53.42Al.sub.2 O.sub.3          2.1     2.1      2.1   2.1B.sub.2 O.sub.3          13.1    10.1     8.1   8.1Na.sub.2 O     19.3    19.3     19.3  19.3K.sub.2 O      0.7     0.7      0.7   0.7MgO            3.0     3.0      5.0   3.0CaO            8.3     11.3     11.3  13.3Fe.sub.2 O.sub.3          0.08    0.08     0.08  0.08KI Index       40.2    40.2     40.2  40.2Liquidus       1511    1661     1712  1759Temperature T.sub.L (° F.)Temp. @ η = 1000 Poise          1627    1630     1645  1639η.sub.TL (Poise)% weight loss  3.73    3.34     4.05______________________________________Constituent\Sample #          8       9        10    11______________________________________SiO.sub.2      52.22   52.22    52.22 52.22Al.sub.2 O.sub.3          2.5     2.5      2.5   2.5B.sub.2 O.sub.3          13.9    10.9     8.9   5.9Na.sub.2 O     19.3    19.3     19.3  19.3K.sub.2 O      0.7     0.7      0.7   0.7MgO            3.0     3.0      3.0   8.0CaO            8.3     11.3     13.3  11.3Fe.sub.2 O.sub.3          0.08    0.08     0.08  0.08KI Index       40.2    40.2     40.2  40.2Liquidus       1453    1667     1751  1793Temperature T.sub.L (° F.)Temp. @ η = 1000 Poise          1620    1619     1626  1661η.sub.TL (Poise)% weight loss  3.44______________________________________Constituent\Sample #          12      13       14    15______________________________________SiO.sub.2      53.69   53.69    53.69 53.69Al.sub.2 O.sub.3          2.0     2.0      2.0   2.0B.sub.2 O.sub.3          14.0    13.0     7.5   7.5Na.sub.2 O     19.3    19.3     17.3  21.3K.sub.2 O      0.7     0.7      0.7   0.7MgO            3.13    3.43     5.73  4.51CaO            7.10    7.80     13.0  10.22Fe.sub.2 O.sub.3          0.08    0.08     0.08  0.08KI Index       40.23   40.23    40.23 40.23Liquidus       1411    1456     1791  1777Temperature T.sub.L (° F.)Temp. @ η = 1000 Poise          1624    1624     1671  1616η.sub.TL (Poise)          30,200  12,300   300% weight loss  3.65    4.24______________________________________Constituent\Sample #          16      17       18______________________________________SiO.sub.2      53.42   53.42    52.22Al.sub.2 O.sub.3          2.1     2.1      2.5B.sub.2 O.sub.3          16.1    13.1     13.9Na.sub.2 O     19.3    19.3     19.3K.sub.2 O      0.7     0.7      0.7MgO            0       0        0CaO            8.3     11.3     11.3Fe.sub.2 O.sub.3          0.08    0.08     0.08KI Index       40.2    40.2     40.2Liquidus       1433    1627     1601Temperature T.sub.L (° F.)Temp. @ η = 1000 Poise          1620    1613     1608η.sub.TL (Poise)% weight loss  3.73    2.67______________________________________ 
    
     As can be seen from the examples, compositions of the present invention provide for increased levels of alumina, while remaining within the proposed KI index biosolubility requirements and maintaining acceptable liquidus temperatures (&lt;1800° F.) and viscosities. Theoretically acceptable compositions for rotary process glass fiber production appear to be possible with 2.5% alumina and as little as 5.9% B 2  O 3 . 
     In addition, the present invention provides for decreasing the amount of B 2  O 3  used in glass compositions. Increased levels of alkaline and alkali oxides are used to partly compensate for the decreased amounts of B 2  O 3  used in the present invention; thereby resulting in compositions that meet both the KI index regulations and can be processed by standard rotary methods. 
     The examples demonstrate that compositions within the present invention can be employed in various quantities to tailor specific properties of the compositions. Examples 1-3 show that compositions ranging from 2-3% Al 2  O 3  and 8-11.9% B 2  O 3  have acceptable liquidus temperatures and viscosities, when the high levels of alkali and alkaline oxides are used, (MgO+CaO)&gt;14 and (K 2  O+Na 2  O)≧20. 
     Examples 4-7 show the effect of decreasing the amount of B 2  O 3  and compensating for the decrease by increasing the MgO and/or CaO concentrations. It appears that at lower levels of B 2  O 3 , substituting MgO for B 2  O 3  may provide for a lower liquidus temperatures than substituting CaO. 
     Examples 8-11 show the range of B 2  O 3  concentrations with 2.5% Al 2  O 3  that have properties within the theoretically acceptable range for rotary processing. Examples 12-15 show a similar comparison for 2.0% Al 2  O 3 . 
     Examples 16-18 show that substituting CaO for B 2  O 3  at higher levels of B 2  O 3  results in a composition with 2.0% Al 2  O 3 . Example 16 is included as a comparative example to demonstrate the unexpectedly increased durability, in addition to an acceptable liquidus temperature and viscosity of the composition of Example 17. The sample composition of Example 18 containing 2.5% Al 2  O 3  also has an acceptable liquidus temperature and viscosity. 
     Generally, the compositions having the highest concentration of B 2  O 3  have the lowest liquidus temperatures (Examples 8, 12, 13, and 16). However, the higher B 2  O 3  concentrations used in the present invention are generally less than the B 2  O 3  concentrations used in the prior art. 
     Unexpectedly, higher durabilities were achieved for compositions in which MgO and/or CaO were substituted for B 2  O 3  (Examples 17 and 5, as compared with Examples 16 and 4, respectively). In addition, the highest durability was achieved in the composition of Example 17, which contained only 2.1% of Al 2  O 3  and had an increased CaO content and correspondingly decreased B 2  O 3  content compared to Example 16. 
     Those of ordinary skill in the art will appreciate that a number of modifications and variations that can be made to specific compositions of the present invention without departing from the scope of the present invention. Such modifications and variations are intended to be covered by the foregoing specification and the following claims.