Abstract
The present invention relates to new glass/polymer composites and methods for making them. More specifically, the invention is glass/polymer composites having phases that are at the molecular level and thereby practicably indistinguishable. The invention further discloses making molecular phase glass/polymer composites by mixing a glass and a polymer in a compatible solvent.
Description
FIELD OF THE INVENTION
The present invention relates generally to new glass/polymer composites and methods for making them. More specifically, the invention relates to glass/polymer composites wherein the interfacing between material constituents or phases is at the molecular level, thereby making the material constituents or phases practicably indistinguishable. The invention further relates to making molecular phase glass/polymer composites by dissolving and mixing glass and polymers in a compatible solvent. BACKGROUND OF THE INVENTION
Polymer/glass or polymer/ceramic composites are known to exhibit superior characteristics compared to non-composite polymer or glass, or ceramic materials taken individually. Improved characteristics include but are not limited to increased thermal stability, chemical stability, and enhanced fracture toughness. This combination of characteristics has made polymer/glass composite materials suitable for uses including but not limited to use as fire retardants. Other uses include but are not limited to lightweight structural applications; for example, optical windows and protective coatings.
The polymer/glass composites are made in two forms. The first form is a glass-phase dispersed material within a polymer carrier matrix material phase as shown by W. A. Bahn and C. J. Quinn, MICROSTRUCTURES OF LOW MELTING TEMPERATURE GLASS/POLYARYLETHERKETONE BLENDS, Preprints, Apr. 5-9, 1991, ANTEC'91, 2730, and the second form is a polymer-phase dispersed material intercalated throughout a glass carrier matrix material phase as demonstrated by E. J. A. Pope et al., TRANSPARENT
SILICA GEL-PMMA COMPOSITES, J. Mat. Res. Soc., 1989 4(4), 1018. In either form, the microstructure of either or both phases persists as the phases are mixed. In other words, there exist discernible bulk phases or islands of dispersed material within the carrier matrix material of the composite.
Either form of these bulk phase polymer/glass composites is made by thermomechanical bulk mixing or diffusion processes. Generally, one or both bulk phase composite constituents are heated and softened, or melted at temperatures ranging from about 380.degree. C. to about 430.degree. C., then mechanically mixed and kneaded at the elevated temperature as taught, for example, by W. A. Bahn et al. Alternatively, a polymer solution may be passed through a porous glass/ceramic matrix leaving the polymer entrained on the pore surfaces as demonstrated by E. J. A. Pope et al.
While bulk phase polymer/glass composites prepared in these ways exhibit the improved properties discussed above, it is believed that the molecular phase glass/polymer composites of the present invention exhibit further improvement in these properties. Moreover, it is expected that the composite material of the present invention will extend performance limits of glass/polymer composites.
The method of making the molecular phase glass/polymer composites requires lower temperatures than the methods for mechanical mixing of bulk phase glass/polymer composites.
SUMMARY OF THE INVENTION
The invention is molecular phase polymer/glass composite materials wherein the phases of carrier matrix material and dispersed material are at the molecular level and thereby practicably indistinguishable. The invention includes methods of making these molecular phase polymer/glass composites.
The method of making these molecular phase polymer/glass composite materials has four basic steps. The first step involves selecting compatible solvents and solutes. The second step is mixing a solution of a glass with a polymer and forming a mixture that is homogeneous at the molecular level. The third step involves removing the solvent while retaining the homogeneous molecular mixture. The fourth step is heating the homogeneous molecular mixture and forming bonds at the molecular level between the glass and the polymer. In addition to the improved mechanical properties of these molecular phase glass/polymer
composites, less energy (both thermal and mechanical) is required for their preparation. Moreover, because solutions are mixed at room temperature, and because the mixture is an intimate mixture, products can be made in a number of ways including but not limited to dip coating, spin casting, melting, casting, and extruding. Products include but are not limited to bulk material products, coatings, films, sheets, and fibers. Further advantages include the use of inexpensive and readily available starting materials or feedstocks and applicability to a wide range of composite compositions.
The subject matter of the present invention is particularly pointed out and distinctly claimed in the concluding portion of this specification. However, both the organization and method of operation, together with further advantages and objects thereof, may best be understood by reference to the following description.
DESCRIPTION OF THE PREFERRED EMBODIMENT(S)
According to a first aspect of the invention, a glass/polymer composite material is made that is a solid solution or molecular phase glass/polymer composite. This solid solution is distinct from a solid mixture because a solid mixture may contain discernible phases of bulk material particles while a solid solution is homogeneously mixed at the molecular level and does not contain distinct phases of bulk material particles. This distinction is further defined by observing that a sectioned surface of a solid mixture composite exhibits microscopically large topographical features, whereas a sectioned surface of a molecular phase glass/polymer composite either appears smooth at the same microscopic magnification or requires substantially greater microscopic magnification to reveal topographical features at a molecular level.
The molecular phase glass/polymer composite material solid solution of the invention has a first solute of at least one glass with a second solute of at least one polymer wherein the first solute and the second solute are homogeneously dispersed at the molecular level. In addition, individual chains of the first solute are chemically bonded to the individual chains of the second solute.
While it may be that the first solute is taken from a particular glass, for example an oxide glass, it will be appreciated by those skilled in the art of glass/polymer composites that the invention is not so limited. The first solute may include other glasses singly or a combination thereof. Glasses may be selected from a group including but not limited to single component
or multi-component oxides (for example phosphate, borate, silica, and silicate glasses), chalcogenides, halides, sulfates, and nitrates. Chalcogenides include but are not limited to sulfur and sulfur containing compounds.
A glass may be made from a network former or a combination of a network former and a network modifier. The type of glass selected depends upon the desired properties of the final product. However, all glasses have molecular networks that, when solubilized, break up into molecular units; for example, open or linear chains or closed chains or rings. In the present invention, linear chains may range in length of backbone from a minimum of about 10 repeat units. For desired physical properties of the glass/polymer composite material, it is preferred that the backbone chain have a length of at least 1,000 repeat units. The maximum number of repeat units depends upon the physical and chemical limitations of the type of glass. Chains having from 10,000 to 100,000 repeat units are practical and are demonstrated in the Examples in this specification. It will be appreciated that the invention is not limited to particular lengths of repeat units of a molecular chain of any particular glass.
Any one glass or combination of glasses may be selected depending upon the properties necessary or desired for a particular product or application.
As for glasses, so it is for polymers that one or a combination may be selected. However, it is preferred that the polymers have long molecular chains wherein the number of repeat units have a correspondence in length to the glass molecular chains. The length correspondence is a parameter that is selectable depending upon the desired properties of the final glass/polymer product, and includes but is not limited to the following two relationships. The correspondence can be a near equality of number of repeat units between glass and polymer molecular chains, or it can be that one chain length is a near integral fraction of the other chain length. Bonding between chains can be one-to-one, but is preferably a randomly intertwined three-dimensional network.
Examples of long chain polymers include but are not limited to organic and inorganic polymers. For this specification, organic polymers are defined as those polymers having only carbon atoms in the backbone chain. Other atoms and functional groups may be attached to the backbone chain. Inorganic polymers, therefore, are polymers having a backbone chain with an atom other than carbon included. Again, other atoms and functional groups may be attached to the backbone chain.
Examples of organic polymers include but are not limited to polyacrylic acid, polyvinyl alcohol, polyvinyl chloride, polyethylene oxide, polyvinyl pyrylidone, carbomethoxy cellulose, water soluble polymers for example polymethacrylic acid, polymeric starches and sugars, and polymers that are soluble in solvents other than water. Examples of inorganic polymers include but are not limited to phosphazenes, siloxanes, silanes, silazanes, and carbosilazenes. Any combination of glass(es) with any polymer(s) may be used as long as there is a solvent in which all constituents are dissolvable.
Molecular phase glass/polymer materials have heretofore been unavailable because there lacked methods for making them. A method of making a molecular phase glass/polymer composite has four basic steps: 1) selecting a solvent then forming a homogeneous mixture of at least one glass solute with at least one polymer solute, 2) removing the solvent and leaving a molecular mixture, then 3) heating the molecular mixture, and 4) producing a solid molecular phase glass/polymer composite.
The first step is selecting a polar solvent. Any polar solvent including but not limited to inorganic polar solvents and organic polar solvents may be used. Inorganic polar solvents include but are not limited to water, mineral acids, liquid ammonia, and thionyl chloride. Organic polar solvents include but are not limited to alcohols, ketones, aromatics, amines, ethers, sulfoxides, and caroxylic acid. The polar solvent selected must have the ability to dissolve both the glass and the polymer, or combination thereof desired for the final product. The preferred solvent is water. Table 1 shows preferred combinations of solvents, glass solutes, and polymer solutes.
The second step is forming a homogeneous mixture of a first solute having at least one glass with a second solute of at least one polymer. The homogeneous mixture is formed by causing to be present within the polar solvent and dissolving in the polar solvent, the first solute and second solute. The glass is caused to be present either by direct dissolution of a glass solid, or by dissolution of a glass precursor followed by hydrolyzing or other glass-forming step to convert the glass precursor to a glass. This mixing step is most preferably carried out under ambient temperature and pressure. However, temperatures and pressures other than ambient may be desirable to impart particular properties to the final product. The preferred operating temperature range is from about the solidification temperature of a component or mixture to about the boiling temperature of a component or mixture. The preferred operating pressure
range is from about hard vacuum, as found in outer space, to about any achievable pressure. The third step is removing the polar solvent. Once the homogeneous mixture is formed under ambient conditions, the long chains of the solutes begin to break into smaller chains. If left from about several hours to about a day, there will be so few long chains remaining, if any, that it is no longer possible to form a molecular glass/polymer composite. It may be that variation in temperature, pressure, or addition of a preservative may retard the breakdown of the long chains, but it is most preferred to proceed with solvent removal within a predetermined time that is as soon as practicable after forming the homogeneous mixture. It is preferred to begin removing solvent within from about several minutes to at most several hours after forming the homogeneous mixture. The amount of time that the homogeneous mixture remains in the solvent is selectable depending upon the desired properties of the final glass/polymer composite material. Where a precipitate is formed, solvent may be removed by pouring or decanting. Where a gel is formed, it is preferred to remove the solvent by evaporating the gel. In either case, removal of the solvent leaves a molecular mixture. When evaporation is used to remove solvent, it may be done by using a low pressure, elevated temperature, or mass transfer concentration differential between the homogeneous mixture and the ambient air. If elevated temperature is used at ambient or elevated pressure, the temperature may range from about 40.degree. C. for six days to about 100.degree. C. for a time less than or about 20 minutes.
The fourth step is heating the molecular mixture and forming bonds between chains of the first and second solutes, thereby producing a solid molecular phase glass/polymer composite wherein composite phases are individual molecules. This heating step may be separate and distinct from the heating used to remove the solvent distinguished by permitting the molecular mixture to cool for a time, or by changing the conditions (temperature and/or pressure) under which the fourth step heating proceeds. Alternatively, the fourth step heating may simply be a continuation in time of the conditions used to remove the solvent. EXAMPLE 1
A first molecular phase glass/polymer composite was made according to the present invention wherein the first solute was an oxide glass of the silica type. The solute was obtained from the precursor tetraethylorthosilicate. The second solute was a polymer polybis(dimethylamino)-phosphazene, and the solvent was ethanol. Water was added as a
reactant,and hydrofluoric acid was added as a catalyst to hydrolyze the precursor to a glass. The ratios by weight of the solutes, solvent, and other components were as follows: 1 part tetraethoxysilane, 4 parts ethanol, 4 parts water, 0.05 parts hydrofluoric acid, and 0.17 parts polybis(dimethylamino)-phosphazene. The ethanol was dried using magnesium ethoxide (Mg(OCH.sub.2 CH.sub.3).sub.2). It is necessary to use a drying process to exclude excess or uncontrollable amounts of water. Upon formation of a homogeneous mixture, a gel was formed. Removal of the solvent from the gel and formation of the solid molecular phase glass/polymer composite was by heating. The gel was heated to a temperature of 40.degree. C. and kept at that temperature for 6 days. The final product was a solid molecular phase glass/phase composite. The process yielded 83% of the theoretical amount of molecular phase glass/polymer composite material. EXAMPLE 2
A second molecular phase glass/polymer composite was made according to the present invention wherein the first solute was a glass sodium metaphosphate (NaPO.sub.3), the second solute was a polymer polybis(dimethylamino)-phosphazene, and the solvent was water. The ratio by weight of the solutes was 1:1. The concentration of both solutes together in the solvent was 10% weight of solutes to volume of solvent (wt/vol).The sodium metaphosphate was obtained from monosodium phosphate monohydrate by heating the monosodium phosphate monohydrate to a temperature of 800.degree. C. , then quenching it between two metal plates.
Removal of the solvent from the homogeneous solution and formation of the solid molecular phase glass/polymer composite was done in two stages. Solvent removal was done by heating the homogeneous solution for 20 minutes at 100.degree. C. Solvent removal was followed by formation of the solid molecular phase by further heating at a temperature of 275.degree. C. for 10 minutes. The amount of solid molecular phase glass/polymer composite was 100% of the theoretical yield.
While a particular ratio of constituents was used for this example, the ratio by weight of sodium metaphosphate solute to polybis(dimethylamino)-phosphazene solute may range from about 1:1 to about 7:1. The amount of the two solutes in proportion to the amount of water solvent may range from a weight ratio that is so small as to be below detectable limits to about 28%, above which there is insufficient solvent to dissolve the solutes. It is preferred
that the lower limit be about 10% since lower concentrations require more heating to remove the water solvent. EXAMPLE 3
A third molecular phase glass/polymer composite was made according to the present invention wherein the first solute was a glass metaphosphate glass (NaLiK(PO.sub.3).sub.3, the second solute was a polymer polybis(dimethylamino)-phosphazene, and the solvent was water. The ratio by weight of the solutes was 1:1. The amount of both solutes in the solvent was 10%(wt/vol).The metaphosphate glass was obtained by mixing equal molar amounts of sodium, lithium, and potassium dihydrogen phosphates, then heating the mixture to a temperature of 800.degree. C. then quenching it between two metal plates. Removal of the solvent from the homogeneous solution and formation of the solid molecular phase glass/polymer composite was by heating. The homogeneous solution was heated to a temperature of 100.degree. C. for 20 minutes, resulting in a molecular mixture. The amount of molecular mixture was 100% of the theoretical yield. Further heating to 275.degree. C. for 10 minutes yielded a solid molecular phase glass/phase composite. EXAMPLE 4
A fourth molecular phase glass/polymer composite was made according to the present invention wherein the first solute was a glass metaphosphate glass NaLiK(PO.sub.3).sub.3, the second and third solutes were a polymer polybis(dimethylamino)-phosphazene and ZnCl.sub.2.H.sub.2 O, and the solvent was water. The ratio by weight of the solutes was 1:1:1.5, respectively. The concentration of the three solutes in the solvent was 10%(wt/vol). The metaphosphate glass was obtained by mixing equal molar amounts of sodium, lithium, and potassium dihydrogen phosphates, then heating the mixture to a temperature of 800.degree. C. , then subsequently quenching it between two metal plates. Removal of the solvent from the homogeneous solution and formation of the solid molecular phase glass/polymer composite was by heating. The homogeneous solution was heated to a temperature of 100.degree. C. for 20 minutes, resulting in a molecular mixture. The amount of molecular mixture was 100% of the theoretical yield. Further heating to 275.degree. C. for 10 minutes yielded a solid molecular phase glass/phase composite. While the amount of zinc chloride was 1.5 times by molar amount the amount of either of the metaphosphate glass in this experiment, the molar amount of zinc chloride may range from about 0.5 to 1.5.
EXAMPLE 5
A fifth molecular phase glass/polymer composite was made according to the present invention wherein the first solute was a metaphosphate glass having a chemical formula of NaKLi(PO.sub.3).sub.3 (1.5(ZnCl.sub.2.H.sub.2 O), the second solute was a polymer polybis(dimethylamino)-phosphazene, and the solvent was water. The ratio by weight of the solutes was 1:1. The concentration of both solutes in the solvent was 10%(wt/vol). The zinc containing metaphosphate glass was similar to Example 5 except that in Example 5 the ZnCl.sub.2.H.sub.2 O was a separate solute whereas in this experiment the ZnCl.sub.2.H.sub.2 O added to the monobasic alkaliphosphates thereby forming a part of the metaphosphate glass solute. The metaphosphate glass was obtained by mixing equal molar amounts of sodium phosphate, lithium phosphate, and potassium phosphate with a 1.5 molar equivalent of ZnCl.sub.2.H.sub.2 O, then heating the mixture to a temperature of 800.degree. C. and quenching it between two metal plates. Removal of the solvent from the homogeneous solution and formation of the solid molecular phase glass/polymer composite was by heating. The homogeneous solution was heated to a temperature of 100.degree. C. for 20 minutes, resulting in a molecular mixture. The amount of molecular mixture was 100% of the theoretical yield. Further heating to 275.degree. C. for 10 minutes yielded a solid molecular phase glass/phase composite. While the amount of zinc chloride was 1.5 times by molar amount the amount of either of the other solutes in this experiment, the molar amount of zinc chloride may range from about 0.5 to 1.5. Alternate Embodiments
The experiments described herein were carried out on a small scale in a laboratory. It will be apparent, however, to those skilled in the art that the molecular phase glass/polymer materials have many uses and the methods of making them including but not limited to spin casting, dip coating, and fiber pulling. Spin casting or dip coating is used for film deposition on a substrate. For spin or dip coating, it is
required that the amount of solutes in solution is between about 2% to 20%(wt/vol) and is preferably from about 2%(wt/vol) to about 5%(wt/vol). The homogeneous mixture of the present invention is deposited onto the substrate to be coated by dipping, then heated to form a solid molecular phase glass/polymer composite coating. Alternatively, the coated substrate may be spun from about 2000 rpm to about 5000 rpm for a time of from about 1 minute to
about 2 minutes. Fiber pulling is done using homogeneous mixtures having from about 10%(wt/vol) to about 50%(wt/vol) of solutes in solution. The pulled fiber is then heated to drive off solvent and produce
a solid molecular phase glass/polymer composite fiber. While several preferred embodiments of the present invention have been shown and described, and several examples have been presented, it will be apparent to those skilled in the art that many changes and modifications may be made without departing from the invention in its broader aspects. The appended claims are therefore intended to cover all such changes and modifications as fall within the true spirit and scope of the invention.
玻璃/聚合物复合材料及其制作方法
【内容摘要】本文主要涉及新的玻璃/聚合物复合材料的介绍以及制作方式。具体地说，本发明是在玻璃/聚合物复合材料的分子水平上分阶段了解其成分从而将其区分。本发明进一步揭示将玻璃与聚合物溶剂混合阶段中玻璃/聚合物复合材料的分子相。
【发明的领域】
本文主要涉及新的玻璃/聚合物复合材料的介绍以及制作方式。更具体地说，本发明是在现有的玻璃/聚合物复合材料的材料成分或材料阶段接口的分子分析水平上，区分其材料成分及阶段。进一步阐释玻璃/聚合物复合材料的溶解与搅拌玻璃和聚合物的溶剂的分子相。
【发明的背景】
对比非复合聚合物或玻璃，陶瓷材料，聚合物/玻璃或聚合物/陶瓷复合材料展示出优越的特性，改进的特征不仅仅是增加热稳定性、化学稳定性和增强断裂韧性，这种组合特点还使得聚合物/玻璃复合材料可以充当阻燃剂使用。除此之外，其用途还不限于轻量级结构应用程序，如光学窗口和防护涂料。
聚合物/玻璃复合材料有两种形式，第一种形式是一个玻璃相以聚合物载体为基质的分散材料，另一种形式是一种聚合物相以玻璃载体为基质的分散材料。在任何一种形态里，微观结构的一种或两种阶段持续的阶段性混合，换句话说，是存在明显的散装阶段或群岛的分散在载体基质材料里的复合。
无论哪一个形式的体相聚合物/玻璃复合材料都是要经过热机的散装混合或扩散过程。一般来说，一个活两个被加热体相的复合成分软化或熔化温度范围从380度到430度左右，然后通过机械混合，或者，聚合物溶液可能通过一个多孔玻璃/陶瓷矩阵离开了聚合物的孔隙表面。
虽然上面所讨论的体相聚合物/玻璃复合材料准备在这些方面表现出改进的属性,本发明展览进一步改善这些分子相玻璃/聚合物复合材料的属性。此外,预计本发明的复合材料将扩展性能限制的玻璃/聚合物复合材料。
分子相玻璃/聚合物复合材料的制作比机械搅拌的体相玻璃/聚合物复合材料需要更低的温度。
【总结】
这项发明是在现有分子水平上，区分分子相聚合物/玻璃复合材料其中阶段的载体
基质和分散的材料,其中还包括区别这些分子相聚合物/玻璃复合材料的方法。
制作这些分子相聚合物/玻璃复合材料的方法有四个基本步骤，首先要选择兼容的溶剂和溶质。第二步是在一定分子水平上将玻璃与聚合物通过混合溶液形成一个均匀的混合物。第三步就是去除溶剂，同时保留均匀分子混合物。第四步是加热均匀分子混合物，形成阶段性分子水平上的玻璃和混合物。
除了改善力学性能的这些分子相玻璃/聚合物复合材料，他们需要准备更少的能量（包括热力和机械）。此外，由于方案实在室温下混合，其混合物为极密混合物，混合产品有多种形式包括浸渍涂料、自旋铸造、熔炼、铸造、挤压。产品包括散装材料产品、涂料、电影、床单和纤维。进一步优化包括使用廉价的和容易获得的起始原料或实用性广泛的复合成分原料。
本发明当前进展主要明确这部分内容的规范。然而这两个组织和操作方法有更多的优势及组合对象，通过以下描述达到更好地理解。
【描述】
根据本发明的第一个方面,玻璃/聚合物复合材料的制成,这是一种固溶体或分子相玻璃/聚合物复合材料。这不同于固溶体的固态混合物，它坚实的解决方案是由于固体混合物可能包含明显的阶段散装材料粒子而在分子水平上均匀混合的,不包含不同阶段的散装材料粒子。这种区别通过观察一个区段的固态混合物表面复合展品显微镜下大体地貌特征,进一步明确一个分段的表面分子相玻璃/聚合物复合要么在同一显微镜放大显得光滑或在分子水平上需要大幅提高显微放大显示地貌。
分子相玻璃/聚合物复合材料固溶体的发明有一个第一溶质至少是一个玻璃与第二个溶质至少是一种聚合物，在该固溶体中的第一个溶质和第二溶质是均匀分散在分子水平上。此外,个别链第一溶质是化学结合到单个链第二溶质。
虽然它第一个溶质可能是一个特定的玻璃,例如一个氧化物玻璃,它将受到那些熟练的艺术玻璃/聚合物复合材料的影响,本发明是没有这样的限制。第一个溶质可能包括其他单独玻璃或组合。玻璃可能会选择一组，单组分或多组分的氧化物(例如磷酸盐、硼酸盐、硅和硅酸盐眼镜),硫属化合物、卤化物、硫酸盐和硝酸盐。硫属化合物包括但不限于硫和含硫化合物。
一个玻璃可能是由一个网络前或结合网络前和一个网络修改器。玻璃的类型选择所需的性能取决于最终产品。然而,所有的玻璃有分子网络,可溶性，可分解为分子单位;例如,打开或关闭或线性链链或环。在本发明,线性链长度范围会的骨干,从最短的大约10重复单位。所要求的物理性质的玻璃/聚合物复合材料,它是首选,主链有一个长
度至少1000重复单位。重复单元的最大数量取决于物理和化学的限制类型的玻璃。链在这个规范中演示了从10000年到100000年重复实际单位和示例，。本发明不限于特定长度重复单位的一个分子链的任何特定玻璃。
任何一个玻璃或组合的玻璃的选择可能会取决其属性的必要或预期对某一特定产品或应用程序的设计。
至于玻璃是如此,对一个或者一组聚合物也可以选择。然而,它是首选,聚合物分子链中一直重复单元的数量中有一个对应的长度与玻璃一致的分子链，它是一个参数的长度,可根据最终的玻璃/聚合物产品的所需性能制定,包括但不仅限于以下两个关系。一是可以接*等数量的重复单位与聚合物分子链之间有联系的玻璃,或者它可能是一个链长度是一个接近积分部分的其他链长度的关系。分子间链可以一对一,但最好是一个随机交织在一起的三维网络。
长链聚合物的例子包括但不限于有机和无机聚合物。对于这个规范,有机聚合物被定义为聚合物只有碳原子链的主干，其他原子和官能团可能连接到主链。因此，无机聚合物主链无碳原子，其他原子和官能团可能连接到主链。有机聚合物的例子包括但不限于聚丙烯酸、聚乙烯醇、聚氯乙烯、聚氧化乙烯、聚乙烯醇等。无极聚合物例子有硅氧烷、硅烷偶联剂、等方面,只要有一个溶剂中所有组分都可溶解的，任何组合的玻璃(es)与任何聚合物(s)可以使用。
若分子相玻璃/聚合物材料保持不可用,那是因为缺少让他们形成的条件。将分子相玻璃/聚合物复合的方法有四个基本步骤：1)选择溶剂然后形成均匀混合，其中至少有一个玻璃溶质与一个高分子溶质,2)去除溶剂并留下一分子混合物，3)加热分子混合物,4)生产固体分子相玻璃/聚合物复合材料。
第一步是选择一个极性溶剂。任何极性溶剂都可以使用不限于无机极性溶剂和有机极性溶剂。无机极性溶剂包括但不限于水、无机酸、液氨、亚硫酰氯。有机极性溶剂包括但不限于醇、酮、芳烃、有机胺类、醚类、酸。极性溶剂的选择必须能够溶解两个玻璃和聚合物,或组合所需要的最终产品。首选的溶剂是水。
第二步是形成一个均匀混合具有至少一个玻璃的第一溶质与有至少一种聚合物第二个溶质。均匀混合物是由极性溶剂和溶解在极性溶剂导致出现在第一和第二溶质中的溶解物。导致玻璃溶解出现要么直接解散一个玻璃固体,或解散一个玻璃前驱。其次是水解或预示着其他玻璃成形的步骤。这种混合步骤是最好是在适宜的环境温度和压力下进行。然而,温度和压力比周围其他可能更需要特定的属性来传授最终产品。首选的工作温度范围为组件的凝固温度或混合物的沸点。首选的操作压力范围为硬真空,层
空间,任何可行的压力。
第三步是移除极性溶剂。一旦在均匀混合形成的环境条件下,长链的溶质开始进入较小的连锁店。如果离开大约几个小时到大约一天,会有那么几个长链出现,任何,剩余的将不再能形成一个分子玻璃/聚合物复合材料。它可能是在温度、压力、或添加防腐剂产生变异,但在预定的时间后,它是长链最优先进行溶剂去除而快速形成的均匀混合物，它从开始移除溶剂的几分钟内到最多几个小时后形成均匀的混合物。一定时间内均匀混合物仍然在溶剂中可根据所需的性能形成最终的玻璃/聚合物复合材料。一个沉淀形成,溶剂可以被浇注或卸载。在凝胶形成,它是首选的蒸发除去溶剂。在这两种情况下，若蒸发是用来去除溶剂,它可能是通过环境空气的低压、高温,或传质浓度差均匀混合物去除溶剂分子混合物。如果提高温度用于环境或高架压力,温度可能范围从一天约40度约到100度并保持6天，且每段时间小于或约等于20分钟。
第四步是分子混合物加热,形成链之间的第一和第二溶质,因此产生了一种固体分子相玻璃/聚合物复合材料中复合阶段的单个分子，这一步可能是分开的,加热用于去除溶剂分子混合物允许冷却一段时间,或通过改变条件(温度和/或压力)。来达到供热收益。另外,第四步加热可能仅仅是一个在时间条件内延续用来除去溶剂的方式。
【示例1】第一个分子相玻璃/聚合物复合材料是根据本发明其中第一溶质是氧化物玻璃的硅类型。溶质获得正硅酸乙酯。第二个溶质是聚合物二醇酯(二甲胺基)磷腈类,溶剂是乙醇。水被添加为反应物,氢氟酸是添加作为催化剂,水解的前体玻璃。按重量的比率的溶质、溶剂和其他组件如下: 1部分四乙氧基硅,4部分乙醇、4部分水,0.05和0.17部分氢氟酸,部分二醇酯(二甲胺基)磷腈类。乙醇是干使用乙醇镁(2 毫克)。因此有必要在干燥过程排除多余或不可控数量的水，从而形成一个均匀混合的凝胶。通过加热去除凝胶溶剂和形成的固体分子相玻璃/聚合物复合材料。这种凝胶加热至温度40度并保持那个温度6天。最终的产品是一个固体分子相和玻璃相复合。这个过程产生了83%的理论量的分子相玻璃/聚合物复合材料。
【示例2】第二个分子相玻璃/聚合物复合材料是根据本发明其中第一溶质是一个玻璃偏磷酸钠(纳波子3),第二个溶质是聚合物二醇酯(二甲胺基)磷腈类,溶剂是水。按重量比的溶质是1:1。溶质的浓度都在一起在溶剂是10%重量的溶质对溶剂量(wt /卷)。得到的偏磷酸钠磷酸钠一水将其加热至800度温度形成单磷酸一水,然后在两个金属板中淬火。在两个阶段中，去除溶剂次解,形成的固体分子相玻璃/聚合物复合材料。溶剂去除是通过加热100度20分钟次解，在溶剂去除之后,形成的固体分子相通过进一步加热,10分钟加热至275度。该数量的固体分子相玻璃/聚合物复合材料的理论产量为
100%。用于此示例的特定的成分比例是,一定重量比的偏磷酸钠溶质与二醇酯(二甲胺基)磷腈类溶质的比重可能范围从约1:1约7:1。溶质的量成比例的两个量的水溶剂,是如此的小,低于检测极限约28%,上面没有足够的溶剂来溶解的溶质。这是首选,下限是大约10%，因为低浓度需要更多的加热去除水溶剂。
【示例3】第三个分子相玻璃/聚合物复合材料是根据本发明其中第一溶质是一个玻璃偏磷酸盐玻璃，第二个溶质是聚合物二醇酯(二甲胺基)磷腈类,溶剂是水。按重量比的溶质是1:1。溶质的量都在溶剂为10%(wt /卷)。这个偏磷酸盐玻璃得到平等的摩尔量的混合钠、锂、磷酸二氢钾,然后加热混合物的温度为800度。然后在两个金属板间淬火。去除溶剂次解,形成的固体分子相玻璃/聚合物复合材料是通过加热均匀溶液至温度100度20分钟,形成分子混合物。这个数量的分子混合物理论产量的100%。进一步加热到275度10分钟产生一个固体分子相玻璃/相复合。
【示例4】第四个分子相玻璃/聚合物复合材料是根据本发明其中第一溶质是一个玻璃偏磷酸盐玻璃。第二个和第三个溶质是聚合物二醇酯(二甲胺基)磷腈类和ZnCl.sub.2.H.sub.2 O,溶剂是水。按重量比的溶质分别是5:5:5。溶质的浓度为溶剂内的10%(wt /卷)。这个偏磷酸盐玻璃得到平等的摩尔量的混合钠、锂、磷酸二氢钾,然后加热混合物的温度为800度,随后在两个金属板间淬火。去除溶剂次解,形成的固体分子相玻璃/聚合物复合材料是通过加热均匀溶液至温度100度20分钟,形成分子混合物。这个数量的分子混合物理论产量的100%。进一步加热到275度 10分钟产生一个固体分子相玻璃/相复合。当一定数量的锌氯是由摩尔量的1.5倍的偏磷酸盐玻璃，在这个实验中,摩尔量的锌氯可能范围为0.5到1.5。
【示例5】第五个分子相玻璃/聚合物复合材料是根据本发明其中第一溶质是一个偏磷酸盐玻璃有化学公式,NaKLi(1.5(ZnCl.sub.2.H.sub。2 O),第二个溶质是聚合物二醇酯(二甲胺基)磷腈类,溶剂是水。按重量比的溶质是1:1。溶质的浓度都在溶剂的10%(wt/卷)。偏磷酸锌含有玻璃类的ZnCl.sub.2.H.sub.2 O，它是一个单独的溶质,而在这个实验中,ZnCl.sub.2.H.sub。2 O 添加到单碱的碱性磷酸盐，从而形成一个部分偏磷酸盐玻璃溶质。这个偏磷酸盐玻璃得到平等的摩尔量的混合磷酸钠,磷酸锂和磷酸钾1.5摩尔当量的ZnCl.sub.2.H.sub.2 O,然后加热混合物的温度至800度和在两个金属板间淬火。去除溶剂次解,形成的固体分子相玻璃/聚合物复合材料，通过加热均匀溶液至100度20分钟,形成分子混合物。这个数量的分子混合物理论产量的100%。进一步加热到275度10分钟产生一个固体分子相玻璃/相复合。锌氯数量是其他溶质的摩尔量的1.5倍，那么在这个实验中,摩尔量的锌氯可能范围从0.5到1.5。
【备用】文中所述的实验明显是在小规模的实验室内进行。然而,那些熟练的艺术,分子相玻璃/高分子材料还有很多使用的方法，其中包括但不限于自旋铸造、浸涂、纤维牵引。自旋铸造或浸渍涂层用于薄膜沉积在基板上，为旋转或浸渍涂层,是必需的,在溶液中溶质的量约为2%到20%之间(wt /卷),最好是约2%(wt /卷)到5%(wt /卷)。均匀混合的本发明表面浸渍沉积到衬底,然后加热到形成一个固体分子相玻璃/聚合物复合涂层。另外,涂层衬底可以从1分钟到2分钟纺成约2000转到5000转。纤维拉丝是通过使用均匀混合物有从约10%(wt /卷)到50%(wt /卷)溶剂在溶液，然后加热的拉纤维来去除溶剂和生产固体分子相玻璃/聚合物复合纤维。而本发明已证明和描述了本文的首选,并给出了几个例子,很显然,那些熟练的艺术,许多变化和修正可以不背离本发明的原理而应用到更广泛的方面。因此这个附加索赔旨在涵盖所有这些变化和修改是属于这个发明的精神范围之内。
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