Patent Application
20230295035
The present invention relates to a microcrystalline glass, in particular to a microcrystalline glass with excellent mechanical properties, a microcrystalline glass product and a method of manufacturing thereof.
In recent years, with the rise and development of consumer electronics, glass has been used in a large number of such electronic devices as a transparent and high performance material. Devices such as LED and LCD displays and computer monitors can have a ‘touch’ function, which makes it necessary for the glass used in them to come into contact with various objects (such as the user's finger and/or stylus device), so that the glass needs to be strong and chemically stable enough to withstand regular contact without damage. In addition, such glass is used in portable electronics, such as mobile phones (handsets), tablets and personal media terminals, where the glass needs to withstand not only the regular ‘touch’ contact from the application for extended periods of time, but also the occasional bending, scratching and impact that may occur during use, which puts forward higher requirements for the relevant properties of glass.
Microcrystalline glass is a material that is crystallised within the glass by heat treatment and has superior mechanical properties to conventional glass. The formation of micro-crystals in the glass gives it a significant advantage over conventional glass in terms of bending, abrasion and drop resistance. On the other hand, microcrystalline glass can also be chemically strengthened to further improve its mechanical properties. Based on the above advantages, microcrystalline glass or its treated microcrystalline glass products are currently used in display devices or electronic devices that require higher resistance to drops, pressure and scratches, especially in the front and rear covers of portable electronic devices (such as mobile phones, watches, PADs, etc.).
With the development of science and technology, electronic devices or display devices have put forward higher requirements for the optical properties of the glass materials used in them. Optical properties refer to the performance of substances in the absorption, reflection and refraction of light, including light transmission rate, haze and refractive index. However, the microcrystalline glass currently on the market has poor chemical strengthening properties, high haze and low light transmission rate, which makes it difficult to be used in demanding display devices or electronic devices.
Therefore, to develop a microcrystalline glass and microcrystalline glass products with excellent mechanical properties and suitable for display devices or electronic devices becomes a goal pursued by scientists.
The technical problem to be solved by the present invention is to provide a microcrystalline glass and microcrystalline glass product with excellent mechanical properties.
The technical solutions used in the present invention to solve the technical problem are:
(91) The matrix glass according to any one of (79)˜(83), wherein the components do not contain SrO; and/or do not contain BaO; and/or do not contain MgO; and/or do not contain CaO; and/or do not contain ZnO; and/or do not contain PbO; and/or do not contain As2O3; and/or do not contain TiO2; and/or do not contain B2O3; and/or do not contain Y2O3; and/or do not contain F.
(155) The method of manufacturing a microcrystalline glass according to any one of (144)˜(149), further the microcrystalline glass comprise the following components by weight percentage: La2O3+Gd2O3+Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2: 0˜5%, preferably La2O3+Gd2O3+Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2: 0˜2%, more preferably La2O3+Gd2O3+Yb2O3+Nb2O5+WO3+Bi2O3+Ta2O5+TeO2+GeO2: 0˜1%.
(156) The method of manufacturing a microcrystalline glass according to any one of (144)˜(149), wherein the components of the microcrystalline glass do not contain SrO; and/or do not contain BaO; and/or do not contain MgO; and/or do not contain CaO; and/or do not contain ZnO; and/or do not contain PbO; and/or do not contain As203; and/or do not contain TiO2; and/or do not contain B2O3; and/or do not contain Y2O3; and/or do not contain F.
The beneficial effect of the present invention is that through a reasonable component design, the microcrystalline glass or microcrystalline glass products obtained by the present invention have excellent mechanical properties.
The microcrystalline glasses and microcrystalline glass product of the present invention are materials with a crystalline phase (sometimes referred to as a crystal) and a glass phase, which are distinct from amorphous solids. The crystalline phase of microcrystalline glasses and microcrystalline glass products can be identified by the angle of the peak appearing in the X-ray diffraction pattern of the X-ray diffraction analysis and/or measured by TEMEDX.
The inventors of the present invention have, after repeated trials and studies, obtained the microcrystalline glass or microcrystalline glass products of the present invention at a lower cost by specifying the content and the proportion of the content of the specific components that make up the microcrystalline glass and microcrystalline glass products to a specific value and by causing them to precipitate a specific crystal phase.
In the following, the ranges of the components (compositions) of the matrix glass, microcrystalline glass and microcrystalline glass product of the present invention are described. In this specification, the content of each component is expressed as a percentage by weight (wt %) of the total substance of the matrix glass, or microcrystalline glass, or microcrystalline glass product, relative to the composition converted to oxide, unless otherwise stated. In this context, the term “converted to oxide composition” refers to the total amount of matter of oxides, complex salts and hydroxides used as raw materials for the composition of the matrix glass, microcrystalline glass or microcrystalline glass products of the present invention, if they decompose and are converted to oxides when melted, as 100% of the total amount of matter of the oxides. In addition, when referred to in this specification as glass only, it is referred to as matrix glass before crystallization (i.e. crystallization process treatment), after crystallization (i.e. crystallization process treatment) of the matrix glass it is referred to as microcrystalline glass, and microcrystalline glass products are products obtained after chemical strengthening of microcrystalline glass.
Unless otherwise indicated in a particular case, the range of values set out herein includes upper and lower limits. As used herein, the term “about” refers to formulations, parameters and other quantities and characteristics that are not, and need not be, exact, but may be approximate and/or greater or lesser if required, reflecting tolerances, conversion factors, measurement errors, etc. The term “and/or” is used herein in an inclusive sense, e.g. “A; and/or B” means that only A, or only B, or both A and B are present.
The crystalline phase in the microcrystalline glass or microcrystalline glass product of the present invention contains a lithium silicate crystalline phase; and/or a lithium phosphate crystalline phase; and/or a petalite crystalline phase; and/or a quartz solid solution crystalline phase.
In some embodiments of the present invention, the crystalline phase in the microcrystalline glass or microcrystalline glass product contains a lithium silicate crystalline phase (one or both of lithium monosilicate and lithium disilicate). In some embodiments, the lithium silicate crystalline phase has a higher weight percentage than the other crystalline phases. In some embodiments, the lithium silicate crystalline phase is 10˜70% by weight of the microcrystalline glass or microcrystalline glass product, preferably lithium silicate crystalline phase is 10˜65% by weight of the microcrystalline glass or microcrystalline glass product, more preferably lithium silicate crystalline phase is 15˜60% by weight of the microcrystalline glass or microcrystalline glass product, further preferably lithium silicate crystalline phase is 20˜55% by weight of the microcrystalline glass or microcrystalline glass product. In some embodiments, the lithium silicate crystalline phase as a percentage by weight of the microcrystalline glass or microcrystalline glass product is 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%.
In some embodiments of the present invention, the crystalline phase in the microcrystalline glass or microcrystalline glass product contains lithium monosilicate crystalline phase. In some embodiments, the lithium monosilicate crystalline phase has a higher weight percentage than the other crystalline phases. In some embodiments, the lithium monosilicate crystalline phase is 30˜65% by weight of the microcrystalline glass or microcrystalline glass product, preferably lithium monosilicate crystalline phase is 35˜60% by weight of the microcrystalline glass or microcrystalline glass product, more preferably lithium monosilicate crystalline phase is 40˜55% by weight of the microcrystalline glass or microcrystalline glass product. In some embodiments, the lithium monosilicate crystalline phase as a percentage by weight of the microcrystalline glass or microcrystalline glass product is 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%.
In some embodiments of the present invention, the crystalline phase in the microcrystalline glass or microcrystalline glass product contains lithium disilicate crystalline phase. In some embodiments, the lithium disilicate crystalline phase has a higher weight percentage than the other crystalline phases. In some embodiments, the lithium disilicate crystalline phase is 10˜60% by weight of the microcrystalline glass or microcrystalline glass product, preferably lithium disilicate crystalline phase is 15˜50% by weight of the microcrystalline glass or microcrystalline glass product, more preferably lithium disilicate crystalline phase is 20˜45% by weight of the microcrystalline glass or microcrystalline glass product. In some embodiments, the lithium disilicate crystalline phase as a percentage by weight of the microcrystalline glass or microcrystalline glass product is 10%, 11%, 12%, 13%. 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%.
In some embodiments of the present invention, the crystalline phase in the microcrystalline glass or microcrystalline glass product contains lithium phosphate crystalline phase, the lithium phosphate crystalline phase is 10% or less by weight of the microcrystalline glass or microcrystalline glass product, and the preferably lithium phosphate crystalline phase is 5% or less by weight of the microcrystalline glass or microcrystalline glass product. In some embodiments, the lithium phosphate crystalline phase as a percentage by weight of the microcrystalline glass or microcrystalline glass product is 0%, above 0%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%.
In some embodiments of the present invention, the crystalline phase in the microcrystalline glass or microcrystalline glass product contains quartz solid solution crystalline phase, the quartz solid solution crystalline phase is 10% or less by weight of the microcrystalline glass or microcrystalline glass product, and the preferably quartz solid solution crystalline phase is 5% or less by weight of the microcrystalline glass or microcrystalline glass product. In some embodiments, the quartz solid solution crystalline phase as a percentage by weight of the microcrystalline glass or microcrystalline glass product is 0%, above 0%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%.
In some embodiments of the present invention, the crystalline phase in the microcrystalline glass or microcrystalline glass product contains petalite crystalline phase, the petalite crystalline phase is 18% or less by weight of the microcrystalline glass or microcrystalline glass product, the preferably petalite crystalline phase is 15% or less by weight of the microcrystalline glass or microcrystalline glass product, the more preferably petalite crystalline phase is 10% or less by weight of the microcrystalline glass or microcrystalline glass product, and the further preferably petalite crystalline phase is 5% or less by weight of the microcrystalline glass or microcrystalline glass product. In some embodiments, the petalite crystalline phase as a percentage by weight of the microcrystalline glass or microcrystalline glass product is 0%, above 0%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%.
SiO2 is a necessary component to form the network structure of the glass of the present invention and is one of the main components for the formation of crystals after heat treatment. If the content of SiO2 is below 55%, the transparency of the microcrystalline glass and microcrystalline glass products formed after the glass crystallization treatment is not high and the formation of crystals in the microcrystalline glass will become less, which affects the body drop height of the microcrystalline glass and the drop resistance of the microcrystalline glass products. Therefore, the lower limit of the SiO2 content is 55%, preferably is 58%, more preferably is 60%. In some embodiments, the lower limit of the preferably SiO2 content is 65%, more preferably is 68%, further preferably is 70%. On the other hand, if the SiO2 content is above 80%, glass forming is difficult, glass is not easily formed, the number of crystal forming species in the microcrystalline glass changes, raising the chilling temperature (Ts) of the microcrystalline glass, affecting the heat bending of glass and microcrystalline glass and having a greater impact on the surface stress and ion exchange layer depth of the microcrystalline glass product. Therefore, the upper limit of SiO2 content is 80%, preferably is 78% and more preferably is 76%. In some embodiments, it may comprise about 55%, 55.5%, 56%, 56.5%, 57%, 57.5%, 58%, 58.5%, 59%, 59.5%, 60%, 60.5%, 61%, 61.5%, 62%, 62.5%, 63%, 63.5%, 64%, 64.5%, 65%, 65.5%, 66%, 66.5%, 67%, 67.5%, 68%, 68.5%, 69%, 69.5%, 70%, 70.5%, 71%, 71.5%, 72%, 72.5%, 73%, 73.5%, 74%, 74.5%, 75%, 75.5%, 76%, 76.5%, 77%, 77.5%, 78%, 78.5%, 79%, 79.5%, 80% SiO2.
Al2O3 can form a glass network structure, which is conducive to the forming of glass, and is conducive to the chemical strengthening of microcrystalline glass, improving the resistance to shattering and the bending strength of microcrystalline glass products; if the content of Al2O3 is too much, it is easy to produce other crystals in the microcrystalline glass and microcrystalline glass products, which in turn leads to the haze of microcrystalline glass and microcrystalline glass products increase. Therefore, the content of Al2O3 in the present invention is below 10%, preferably 0.1˜8%, more preferably 0.5˜7%. In some embodiments, the content of preferably Al2O3 is below 5%, more preferably 0.1˜4.5%, further preferably 0.5˜3%. In some embodiments, about 0%, above 0%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7%, 7.1%, 7.2%, 7.3%, 7.4%, 7.5%, 7.6%, 7.7%, 7.8%, 7.9%, 8%, 8.1%, 8.2%, 8.3%, 8.4%, 8.5%, 8.6%, 8.7%, 8.8%, 8.9%, 9%, 9.1%, 9.2%, 9.3%, 9.4%, 9.5%, 9.6%, 9.7%, 9.8%, 10% of Al2O3 may be included.
Li2O can promote the melting of glass, reduce the melting temperature of glass, can reduce the partitioning of P2O5, promote the dissolution of P2O5, is the main component of microcrystalline glass and microcrystalline glass products to form crystals, and is also a component of chemical strengthening mainly with sodium and potassium ions for replacement, can increase the surface stress of microcrystalline glass products, enhance the height of the falling ball test of microcrystalline glass products and can increase the dielectric constants of microcrystalline glass and microcrystalline glass product. However, if the Li2O content is below 8%, the formation of the lithium silicate crystalline phase is poor and affects the depth of the ion exchange layer in the microcrystalline glass product, affecting the drop ball test height and fragmentation of the microcrystalline glass and microcrystalline glass product. Accordingly, the lower limit of Li2O content is 8%, preferably 9%, more preferably 10%. In some embodiments, the lower limit of the further preferably Li2O is 12.5%. On the other hand, if too much Li2O is present, the glass tends to phase during the crystallization process, affecting the light transmission of the microcrystalline glass and microcrystalline glass products. Therefore, the upper limit of the Li2O content is 25%, preferably 22%, more preferably 20%. In some embodiments, it is possible to include about 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, 24%, 24.5%, 25% Li2O.
It has been found through extensive experimental studies by the inventors that in some embodiments of the present invention, the crystallinity of microcrystalline glass and microcrystalline glass products can be improved and the grain size of microcrystalline glass and microcrystalline glass products can be reduced by controlling the ratio Al2O3/Li2O between the content of Al2O3 and the content of Li2O at 0.7 or less. Thus, the preferably Al2O3/Li2O is 0.7 or less, and the more preferably Al2O3/Li2O is 0.6 or less. Further, in some embodiments, by controlling Al2O3/Li2O at 0.5 or less, the light transmission of the microcrystalline glass and microcrystalline glass products can also be optimized and the haze of the microcrystalline glass and microcrystalline glass products can be reduced. Thus, the further preferably Al2O3/Li2O is 0.5 or less and much further preferably Al2O3/Li2O is 0.45 or less. In some embodiments, preferably Al2O3/Li2O is 0.4 or less, more preferably Al2O3/Li2O is 0.3 or less, further preferably Al2O3/Li2O is 0.2 or less, much further preferably Al2O3/Li2O is 0.1 or less. In some embodiments, the value of Al2O3/Li2O may be 0, above 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48 0.47, 0.48, 0.49, 0.5, 0.55, 0.6, 0.65, 0.7.
Na2O can lower the melting temperature of the glass and can effectively reduce the exchange rate of Li and Na during the chemical strengthening of microcrystalline glass, making the chemical strengthening process easier to control. The lower limit of preferably Na2O content is 0.5%. On the other hand, if too much Na2O is contained, it affects the formation of crystals in the microcrystalline glass and reduces the crystallinity of the microcrystalline glass and microcrystalline glass products, leading to a reduction in the strength of the microcrystalline glass and microcrystalline glass products. Therefore, the content of Na2O is 0 to 6%, preferably 0 to 4%, more preferably 0.5 to 3%. In some embodiments, about 0%, above 0%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6% of Na2O may be included.
K2O reduces the viscosity of the glass and promotes crystal formation during the crystallization process treatment, but if too much K2O is present, it tends to coarsen the crystals of the microcrystalline glass and microcrystalline glass products and reduces the light transmission rate and the height of the drop ball test of the microcrystalline glass and microcrystalline glass products. Therefore, the upper limit of K2O is 5%, preferably is 4% and more preferably is 2%. In some embodiments, about 0%, above 0%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% of K2O may be included.
P2O5 in the present invention can promote the formation of crystals, improve the crystallinity of microcrystalline glass and microcrystalline glass products, increase the hardness and strength of microcrystalline glass and microcrystalline glass products, and reduce the haze of microcrystalline glass and microcrystalline glass products. The lower limit of P2O5 content in the present invention is 1%, preferably 1.5%, more preferably 2%. On the other hand, if too much P2O5 is contained, uneven crystal distribution forms when the glass is formed, making it difficult to control the haze and strength of the microcrystalline glass after heat treatment, and reducing the chemical stability of the glass. Therefore, the upper limit of P2O5 content is 8%, preferably 7% and more preferably 6%. In some embodiments, about 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% of P2O5 may be included.
In the present invention, ZrO2 and P2O5 cooperate with each other to refine the grain, reduce the haze of microcrystalline glass and microcrystalline glass products, ZrO2 can increase the network structure of the glass, which is conducive to the chemical strengthening of microcrystalline glass, increase the depth of the ion exchange layer of microcrystalline glass products and improve the height of the drop ball test of microcrystalline glass products. Therefore, the lower limit of ZrO2 content is 5%, preferably 6% and more preferably 7%. On the other hand, if too much ZrO2 is present, glass melting is difficult. Therefore, the upper limit of the ZrO2 content is 15%, preferably 12%. In some embodiments, about 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15% of ZrO2 may be included.
In some embodiments, by controlling the ratio SiO2/ZrO2 between the content of SiO2 and ZrO2 in the range of 4.0˜15.8, the haze and |B| values of the microcrystalline glass after heat treatment (e.g. heat bending) can be further optimized for superior haze and |B| values of the microcrystalline glass and microcrystalline glass products after heat treatment (e.g. heat bending). Therefore, preferably SiO2/ZrO2 range is 4.0˜15.8, and more preferably SiO2/ZrO2 is 4.5˜12.0. Further, in some embodiments, by making the SiO2/ZrO2 in the range of 5.0˜9.5, it is also possible to increase the ion exchange layer depth of the microcrystalline glass products and improve the resistance of the microcrystalline glass products, and therefore further preferably SiO2/ZrO2 is 5.0˜9.5, and much further preferably SiO2/ZrO2 is 6.0˜9.0. In some embodiments, the value of SiO2/ZrO2 may be 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, 15.0, 15.5, 15.8.
In some embodiments, the combined content of P2O5 and ZrO2, P2O5+ZrO2 is in the range of 6˜21%, which reduces the haze of microcrystalline glass (including microcrystalline glass after heat bending) and microcrystalline glass products. Thus, preferably P2O5+ZrO2 is 6˜21%, and more preferably P2O5+ZrO2 is 7˜18%. Further, in some embodiments, the fracture toughness of the microcrystalline glass product can also be increased by having P2O5+ZrO2 in the range of 8˜16%. Thus, the further preferably P2O5+ZrO2 is 8˜16%, and much further preferably P2O5+ZrO2 is 10˜16%. In some embodiments, the value of P2O5+ZrO2 may be 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15%, 15.5%, 16%, 16.5%, 17%, 17 17.5%, 18%, 18.5%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%.
In some embodiments, by controlling the ratio of Al2O3/(P2O5+ZrO2) between Al2O3 and the combined content of P2O5 and ZrO2 to be 1.2 or less, the crystalline phase content of lithium disilicate in the microcrystalline glass can be increased and the body drop height of the microcrystalline glass and the drop ball test height of the microcrystalline glass product can be increased. Therefore, preferably Al2O3/(P2O5+ZrO2) is 1.2 or less, more preferably Al2O3/(P2O5+ZrO2) is 1.0 or less, and further preferably Al2O3/(P2O5+ZrO2) is 0.05˜0.7. Further, in some embodiments, by making Al2O3/(P2O5+ZrO2) in the range of 0.1˜0.6, the haze of the microcrystalline glass and microcrystalline glass products can also be reduced, so much further preferably Al2O3/(P2O5+ZrO2) is 0.1˜0.6. In some embodiments, the value of Al2O3/(P2O5+ZrO2) can be 0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2.
In some embodiments, by controlling the ratio of SiO2/(P2O5+ZrO2) between SiO2 and the combined content of P2O5 and ZrO2 in the range of 2.5˜12.0 can promote the formation and increase the content of the lithium silicate crystalline phase in the microcrystalline glass and inhibit the formation of other crystalline phases, which can effectively ensure the heat bendability of the microcrystalline glass by heat treatment and improve the heat bending performance of microcrystalline glass. Therefore, the range of preferably SiO2/(P2O5+ZrO2) is 2.5˜12.0, and more preferably SiO2/(P2O5+ZrO2) is 3.0˜10.0. Further, in some embodiments, by making the SiO2/(P2O5+ZrO2) in the range of 3.5˜7.5, the crystallinity of the microcrystalline glass and microcrystalline glass products can also be improved, increasing the fragmentation of the microcrystalline glass products after fracture. Therefore, the range of further preferably SiO2/(P2O5+ZrO2) is 3.5˜7.5 and much further preferably SiO2/(P2O5+ZrO2) is 4.0˜6.5. In some embodiments, the value of SiO2/(P2O5+ZrO2) may be 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0.
In some embodiments, making the ratio of (ZrO2+Li2O)/Al2O3 between the combined content of Li2O and ZrO2 and the content of Al2O3 being 2.0 or more, can increases the dielectric constant of the microcrystalline glass and microcrystalline glass products and facilitates subsequent applications. Thus, the range of (ZrO2+Li2O)/Al2O3 is 2.0 or more, more preferably (ZrO2+Li2O)/Al2O3 is 2.5 or more, and further preferably (ZrO2+Li2O)/Al2O3 is 2.5˜30.0. Further, in some embodiments, by making the (ZrO2+Li2O)/Al2O3 in the range of 3.0˜20.0 range, the dielectric loss of the microcrystalline glass and microcrystalline glass products can also be reduced. Thus, much further preferably (ZrO2+Li2O)/Al2O3 is in the range of 3.0˜20.0. In some embodiments, the value of (ZrO2+Li2O)/Al2O3 may be 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, 15.0, 15.5, 16.0, 16.5, 17.0, 17.5, 18.0, 18.5, 19.0, 19.5, 20.0, 20.5, 21.0, 21.5, 22.0, 22.5, 23.0, 23.5, 24.0, 24.5, 25.0, 25.5, 26.0, 26.5, 27.0, 27.5, 28.0, 28.5, 29.0, 29.5, 30.0, 31.0, 32.0, 33.0, 34.0, 35.0, 36.0, 37.0, 38.0, 39.0, 40.0, 41.0, 42.0, 43.0, 44.0, 45.0, 46.0, 47.0, 48.0, 49.0, 50.0, 51.0, 52.0, 53.0, 54.0, 55.0, 56.0, 57.0, 58.0, 59.0, 60.0.
In some embodiments of the present invention, making the ratio of (SiO2+Al2O3)/ZrO2 between the combined content of SiO2, Al2O3 and the content of ZrO2 in the range of 4.0˜16.0, can allows the microcrystalline glass and microcrystalline glass products to have a suitable surface resistance for subsequent use. Therefore, it is preferred that (SiO2+Al2O3)/ZrO2 is 4.0˜16.0, more preferably (SiO2+Al2O3)/ZrO2 is 4.5˜12.0. Further, in some embodiments, by controlling (SiO2+Al2O3)/ZrO2 in the range of 5.0˜10.0, the change of crystalline phase content of glass ceramics after further heat treatment (such as hot bending) can be reduced, which is conducive to controlling the size of microcrystalline glass after heat treatment (such as hot bending) and facilitating subsequent processing. Therefore, preferably (SiO2+Al2O3)/ZrO2 is 5.0˜10.0, and more preferably (SiO2+Al2O3)/ZrO2 is 6.0˜9.5. In some embodiments, the value of (SiO2+Al2O3)/ZrO2 may be 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5, 14.0, 14.5, 15.0, 15.5, 16.0.
Extensive experimental studies by the inventors have revealed a complex synergistic effect of Al2O3, Li2O, ZrO2 and P2O5. In some embodiments of the present invention, the drop ball test height of microcrystalline glass and microcrystalline glass products can be improved by controlling Al2O3/(Li2O+ZrO2+P2O5) to be 0.4 or less, thus preferably Al2O3/(Li2O+ZrO2+P2O5) to be 0.4 or less, more preferably Al2O3/(Li2O+ZrO2+P2O5) to be 0.3 or less, further preferably Al2O3/(Li2O+ZrO2+P2O5) is 0.25 or less. In some embodiments, by controlling Al2O3/(Li2O+ZrO2+P2O5) in the range of 0.01˜0.2, the haze and light transmission of the microcrystalline glass and microcrystalline glass products can also be optimized. Therefore, much further preferably Al2O3/(Li2O+ZrO2+P2O5) is in the range of 0.01˜0.2, and much more further preferably Al2O3/(Li2O+ZrO2+P2O5) is in the range of 0.01˜0.1. In some embodiments, the value of Al2O3/(Li2O+ZrO2+P2O5) may be 0, above 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4.
In some embodiments of the present invention, the hardness and drop ball test height of the microcrystalline glass and microcrystalline glass products can be improved by making the ratio of (Li2O+ZrO2)/SiO2 between the combined content of Li2O, ZrO2 and the content of SiO2 in the range of 0.19˜0.55. Thus, preferably (Li2O+ZrO2)/SiO2 is in the range of 0.19˜0.55, more preferably (Li2O+ZrO2)/SiO2 is in the range of 0.2˜0.5. Further, in some embodiments, the |B| value of the microcrystalline glass and microcrystalline glass products can also be reduced by having (Li2O+ZrO2)/SiO2 in the range of 0.25˜0.45. Thus, more preferably (Li2O+ZrO2)/SiO2 is in the range of 0.25˜0.45, and further preferably (Li2O+ZrO2)/SiO2 is in the range of 0.25˜0.4. In some embodiments, the value of (Li2O+ZrO2)/SiO2 may be 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.5, 0.51, 0.52, 0.53, 0.54, 0.55.
In some embodiments of the present invention, the bending strength of the microcrystalline glass and microcrystalline glass products can be improved by controlling the ratio of (Li2O+Al2O3)/ZrO2 between the combined content of Li2O, Al2O3 and the content of ZrO2 in the range of 0.8˜5.0. Therefore, preferably (Li2O+Al2O3)/ZrO2 is in the range of 0.8˜5.0, and more preferably (Li2O+Al2O3)/ZrO2 is in the range of 1.0˜4.0. Further, by controlling (Li2O+Al2O3)/ZrO2 to be in the range of 1.2˜3.0, the chemical strengthening properties of the microcrystalline glass can be further optimized and the depth of the ion exchange layer and surface stress of the microcrystalline glass products can be improved. Thus, further preferably (Li2O+Al2O3)/ZrO2 is 1.2˜3.0, and much further preferably (Li2O+Al2O3)/ZrO2 is 1.5˜2.5. In some embodiments, the value of (Li2O+Al2O3)/ZrO2 may be 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0.
In some embodiments of the present invention, the |B| value and grain size of the microcrystalline glass and microcrystalline glass products can be reduced by controlling the ratio of Li2O/(ZrO2+P2O5) between the content of Li2O to the combined content of ZrO2 and P2O5 in the range of 0.5—′3.0. Therefore, preferably Li2O/(ZrO2+P2O5) is in the range of 0.5˜3.0, and more preferably Li2O/(ZrO2+P2O5) is in the range of 0.6˜2.5. Further, by making Li2O/(ZrO2+P2O5) in the range of 0.7˜2.0, the chemical strengthening properties of the microcrystalline glass can be optimized, the ion-exchange layer depth and the fracture toughness of the microcrystalline glass product can be improved. Thus, further preferably Li2O/(ZrO2+P2O5) is in the range of 0.7˜2.0, and much further preferably Li2O/(ZrO2+P2O5) is in the range of 0.8˜1.5. In some embodiments, the value of Li2O/(ZrO2+P2O5) may be 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2.0, 2.05, 2.1, 2.15, 2.2, 2.25, 2.3, 2.35, 2.4, 2.45, 2.5, 2.55, 2.6, 2.65, 2.7, 2.75, 2.8, 2.85, 2.9, 2.95, 3.0.
ZnO reduces the difficulty of melting glass and, in excessive amounts, can promote low-temperature phase separation of glass and reduce the crystallinity of microcrystalline glass and microcrystalline glass products. In the present invention, the upper limit of ZnO content is 3%, preferably 2%, more preferably 1%, and further preferably no ZnO. In some embodiments, it may comprise about 0%, above 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3% of ZnO.
MgO reduces the melting difficulty of the glass and facilitates an increase in the drop ball test height of the microcrystalline glass and microcrystalline glass products, but MgO tends to promote low temperature crystallization of the glass and reduces the crystallinity and light transmission of the microcrystalline glass and microcrystalline glass products. Thus, the upper limit of MgO content is 3%, preferably 2%, more preferably 1%, and further preferably no MgO. In some embodiments, it may comprise about 0%, above 0%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3% of MgO.
In some embodiments of the present invention, the hardness, bending strength and fracture toughness of microcrystalline glass and microcrystalline glass products can be improved by controlling the ratio of (MgO+ZnO)/ZrO2 between the combined content of MgO and ZnO to the content of ZrO2 to be 0.65 or less. Thus, preferably (MgO+ZnO)/ZrO2 is 0.65 or less, more preferably (MgO+ZnO)/ZrO2 is 0.4 or less, further preferably (MgO+ZnO)/ZrO2 is 0.2 or less, and much further preferably (MgO+ZnO)/ZrO2 is 0.1 or less. In some embodiments, the value of (MgO+ZnO)/ZrO2 may be 0, above 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.23, 0.25, 0.27, 0.3, 0.33, 0.35, 0.37, 0.4, 0.43, 0.45, 0.47, 0.5, 0.53, 0.55, 0.57, 0.6, 0.63, 0.65.
SrO is an optional component for improving the low temperature melting properties of glass and inhibiting precipitation during glass forming, but too much of it is detrimental to glass forming. Therefore, the SrO content in the present invention ranges 0˜5%, preferably 0˜2%, more preferably 0˜1%, and further preferably without SrO. In some embodiments, it may contain about 0%, above 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% of SrO.
BaO is an optional component that contributes to the glass-forming properties of the glass, and is detrimental to glass forming when present in excessive amounts. Therefore, the BaO content in the present invention ranges 0˜5%, preferably 0˜2%, more preferably 0˜1%, and further preferably without BaO. In some embodiments, it may contain about 0%, above 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% of BaO.
CaO can increase the hardness of the glass, and in excessive amounts, the glass tends to be milky when molded. Therefore the CaO content in the present invention ranges 0˜5%, preferably 0˜2%, more preferably 0˜1%, and further preferably without CaO. In some embodiments, it may contain about 0%, above 0%, 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% of CaO.
TiO2 is an optional component that helps to lower the melting temperature and improve the chemical stability of the glass. The invention contains 5% or less of TiO2, which can make the crystallization process of glass easy to control, preferably with a TiO2 content of 2% or less, more preferably 1% or less. In some embodiments, further preferably no TiO2. In some embodiments, it may contain about 0%, above 0%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% of TiO2.
B2O3 improves the network structure of the glass and adjusts the chemical strengthening properties of the microcrystalline glass. If its content exceeds 5%, it is not conducive to glass forming and tends to precipitate during forming, therefore the upper limit of B2O3 content is 5%, preferably 3%, more preferably 2%, further preferably no B2O3. In some embodiments, it may comprise about 0%, above 0%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% of B2O3.
Y2O3 can promote the melting of ZrO2 and reduce the melting difficulty of glass. Excessive content will lead to difficulties in forming crystals when crystallizing glass, a decrease in the crystallinity of microcrystalline glass and microcrystalline glass products, and a decrease in the height of the falling ball test of microcrystalline glass and microcrystalline glass products. Thus, the upper limit of Y2O3 content is 6%, preferably 4%, and more preferably 2%. In some embodiments, it may contain about 0%, above 0%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6% of Y2O3.
In some embodiments, the glass, microcrystalline glass or microcrystalline glass product may also contain 0 to 2% of a fining agent to improve the defoaming ability of the glass, microcrystalline glass or microcrystalline glass product, the fining agent including but not limited to one or more of Sb2O3, SnO2, SnO, CeO2, F (fluorine), CI (chlorine) and Br (bromine), preferably Sb2O3 as the fining agent. The above fining agents, when present alone or in combination, are preferably present in an upper limit of 1%, more preferably 0.5%. In some embodiments, the content of one or more of the above fining agents is about 0%, above 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%.
Other components not mentioned above, such as La2O3, Gd2O3, Yb2O3, Nb2O5, WO3, Bi2O3, Ta2O5, TeO2, GeO2, etc., may be added as appropriate without affecting the performance of the glass, microcrystalline glass or microcrystalline glass product of the present invention, but preferably, in order to maintain the excellent performance of the glass, microcrystalline glass or microcrystalline glass product of the present invention application, the respective or combined content of La2O3, Gd2O3, Yb2O3, Nb2O5, WO3, Bi2O3, Ta2O5, TeO2, and GeO2 is below 5%, more preferably below 2%, further preferably below 1%, and much further preferably not contained.
PbO and As2O3 are toxic substances and even small amounts of them are not environmentally friendly, so the present invention preferably does not contain PbO and As2O3 in some embodiments.
In some embodiments of the present invention, a matrix glass, microcrystalline glass, or microcrystalline glass product with color can be prepared by containing a colorant that can give the matrix glass, microcrystalline glass, or microcrystalline glass product a different color, the colorant containing: NiO: 0˜4%; and/or Ni2O3: 0˜4%; and/or CoO: 0˜2%; and/or Co2O3: 0˜2%; and/or Fe2O3: 0˜7%; and/or MnO2: 0˜4%; and/or Er2O3: 0˜8%; and/or Nd2O3: 0˜8%; and/or Cu2O: 0˜4%; and/or Pr2O5: 0˜8%; and/or CeO2: 0˜4%. The weight percentage content of the colorants and their effects are detailed as follows:
The brown or green matrix glass, microcrystalline glass or microcrystalline glass products prepared by the present invention use NiO, Ni2O3 or Pr2O5 as colorants. NiO and Ni2O3 are colorants for the preparation of brown or green matrix glass, microcrystalline glass or microcrystalline glass products, and the two components can be used alone or mixed. Their respective contents are generally 4% or less, preferably 3% or less, and if the content exceeds 4%, the colorant is not well soluble in the matrix glass, microcrystalline glass or microcrystalline glass products. The lower limit of their respective contents is 0.1% or more, if below 0.1%, the color of the matrix glass, microcrystalline glass or microcrystalline glass products is not obvious. In some embodiments, it may comprise about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% of NiO or Ni2O3. If used in combination, the combined amount of NiO and Ni2O3 is generally 4% or less, with the lower limit of the combined amount being 0.1% or more. In some embodiments, it may comprise about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3% 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% NiO and Ni2O3. The Use of Pr2O5 as a colorant for green matrix glass, microcrystalline glass or microcrystalline glass products, alone, generally contains 8% or less, preferably 6% or less, with a lower limit of 0.4% or more. If below 0.4%, the color of the matrix glass, microcrystalline glass, or microcrystalline glass product is not apparent. In some embodiments, it may comprise about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, 8.0% of Pr2O5.
The blue matrix glass, microcrystalline glass or microcrystalline glass products prepared by the present invention use CoO or Co2O3 as the colorant, the two colorants components can be used alone or mixed, their respective contents are both generally 2% or less, preferably 1.8% or less. If the content exceeds 2%, the colorant cannot be well dissolved in the matrix glass, microcrystalline glass or microcrystalline glass products. The lower limit of its content is 0.05% or more respectively. If it is below 0.05%, the color of the matrix glass, microcrystalline glass or microcrystalline glass product is not apparent. In some embodiments, about 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0% of CoO or Co2O3 may be included. If used in combination, the combined amount of CoO and Co2O3 does not exceed 2%, with the lower limit of the combined amount being 0.05% or more. In some embodiments, about 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0% of CoO and Co2O3 may be included.
The yellow matrix glass, microcrystalline glass or microcrystalline glass products prepared by the present invention use Cu2O or CeO2 as the colorant, the two colorants components are used alone or mixed, their respective lower limit of content is 0.5% or more. If below 0.5%, the color of the matrix glass, microcrystalline glass or microcrystalline glass products is not obvious, the use of Cu2O alone is 4% or less, preferably 3% or less. If the content exceeds 4%, it tends to precipitate the matrix glass. In some embodiments, about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% of Cu2O may be included. The CeO2 content alone is generally 4% or less, preferably 3% or less. If the content exceeds 4%, the matrix glass, microcrystalline glass or microcrystalline glass product is not glossy. In some embodiments, about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% of CeO2 may be included. Also, a small amount of CeO2 is added to the glass to have a defoaming effect. CeO2 can also be used as a fining agent in glass at an amount of 2% or less, preferably 1% or less, and more preferably 0.5% or less, when used as a fining agent. If the two colorants are mixed, the combined amount is generally 4% or less and the lower limit of the combined amount is 0.5% or more. In some embodiments, about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% of CeO2 and Cu2O may be included.
The black or smoky gray matrix glass, microcrystalline glass or microcrystalline glass products prepared by the present invention use Fe2O3 alone as a colorant; or a mixture of two colorants, Fe2O3 and CoO; or a mixture of two colorants, Fe2O3 and Co2O3; or a mixture of three colorants, Fe2O3, CoO and NiO; or a mixture of Fe2O3, Co2O3 and NiO. Colorants for the preparation of black and smoky gray matrix glass, microcrystalline glass or microcrystalline glass products are mainly colored with Fe2O3 at a content of 7% or less, preferably 5% or less, with a lower limit of 0.2% or more. In some embodiments, about 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0% of Fe2O3. CoO and Co2O3 have absorption in visible light and can deepen the coloration of matrix glass, microcrystalline glass or microcrystalline glass products, generally at a level of 0.6% or less of each when mixed with Fe2O3, with a lower limit of 0.2% or more. In some embodiments, it may comprise about 0.2%, 0.3%, 0.4%, 0.5%, 0.6% of CoO and/or Co2O3. NiO absorbs in visible light and can deepen the coloration of the matrix glass, microcrystalline glass or microcrystalline glass product, generally in a mixture of 1% or less and with a lower limit of 0.2% or more in the aggregate. In some embodiments, about 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0% of NiO may be included.
The purple matrix glass, microcrystalline glass or microcrystalline glass products prepared by the present invention use MnO2 as a colorant, using a content generally 4% or less, preferably 3% or less, with a lower limit of 0.1% or more, if below 0.1%, the color of the matrix glass, microcrystalline glass or microcrystalline glass products is not obvious. In some embodiments, about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% of MnO2 may be included.
The pink matrix glass, microcrystalline glass or microcrystalline glass products prepared by the present invention use Er2O3 as a colorant, using a content of generally 8% or less, preferably 6% or less. Due to the low coloring efficiency of the rare earth element Er2O3, when the used content exceeds 8%, it also cannot make the matrix glass, microcrystalline glass or microcrystalline glass products further deepen the color, but rather increase the cost. The lower limit of its content is 0.4% or more, if below 0.4%, the matrix glass, microcrystalline glass or microcrystalline glass products color is not obvious. In some embodiments, about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, 8.0% of Er2O3 may be included.
The purple-red matrix glass, microcrystalline glass or microcrystalline glass products prepared by the present invention use Nd2O3 as the colorant, using a content generally 8% or less, preferably 6% or less. Because of the low coloring efficiency of rare earth element Nd2O3, the use of content above 8%, also cannot make the matrix glass, microcrystalline glass or microcrystalline glass products to further deepen the color, but to increase the cost. The lower limit of its content is 0.4% or more, if below 0.4%, the matrix glass, microcrystalline glass or microcrystalline glass products color is not obvious. In some embodiments, about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, 8.0% of Nd2O3 may be included.
The present invention prepares red matrix glass, microcrystalline glass or microcrystalline glass products, using Er2O3, Nd2O3 and MnO2 mixed colorant. εr ions in glass have absorption at 400˜500 nm, Mn ions have absorption mainly at 500 nm, Nd ions have strong absorption mainly at 580 nm, the mixture of the three substances can prepare red matrix glass, microcrystalline glass or microcrystalline glass products, due to Er2O3 and Nd2O3 for rare earth coloring, coloring ability is relatively weak, Er2O3 use within 6%, Nd2O3 use within 4%, MnO2 coloring strong, the use of 2% range, the lower limit of its use of mixed colorants combined amount of 0.9% or more.
“Does not contain” “0%” as documented herein means that the compound, molecule or element, etc. was not intentionally added as a raw material to the matrix glass, microcrystalline glass or microcrystalline glass product of the present invention. However, as raw materials and/or equipment for the production of matrix glass, microcrystalline glass or microcrystalline glass products, there will be certain impurities or components that are not intentionally added and will be contained in small amounts or traces in the final matrix glass, microcrystalline glass or microcrystalline glass products, and such cases are also within the scope of protection of the patent of the present invention.
In some embodiments of the present invention, the crystalline phase in the microcrystalline glass and microcrystalline glass products contains lithium monosilicate, which provides high strength to the microcrystalline glass and microcrystalline glass products of the present invention, and the fracture toughness of the microcrystalline glass and microcrystalline glass products becomes high; the height of the drop ball test and four-point bending strength of the microcrystalline glass and microcrystalline glass products become high. The microcrystalline glass of the present invention has excellent chemical strengthening performance, and can also be treated by chemical strengthening process to obtain excellent mechanical strength. Through reasonable component design, the microcrystalline glass and microcrystalline glass products of the present invention can obtain suitable grain size, so that the microcrystalline glass and microcrystalline glass products of the present invention have high strength. The microcrystalline glass and microcrystalline glass products of the present invention have good crystallinity, so that the microcrystalline glass and microcrystalline glass products of the present invention have excellent mechanical properties. The crystallinity refers to the degree of crystalline integrity. The arrangement of particles inside the crystal with complete crystallization is relatively regular, the diffraction lines are strong, sharp and symmetrical, and the half-height width of diffraction peaks is close to the width measured by the instrument; crystals with poor crystallinity have defects such as dislocations, which make the diffraction line peaks wide and diffuse. The weaker the crystallinity, the weaker the diffraction ability and the wider the diffraction peaks until they disappear into the background. In some embodiments, the crystallinity of the microcrystalline glass product or microcrystalline glass is 50% or more, preferably 60% or more, more preferably 70% or more.
The size and type of grains in the microcrystalline glass or microcrystalline glass products of the present invention affect the haze and transmittance of the microcrystalline glass or microcrystalline glass products, the smaller the grains the higher the transmittance; the smaller the haze, the higher the transmittance. In some embodiments, the haze of microcrystalline glass products or microcrystalline glass of thickness 1 mm or less is 0.2% or less, preferably 0.18% or less, more preferably 0.15% or less. In some embodiments, the microcrystalline glass product or microcrystalline glass has a grain size of 80 nm or less, preferably 50 nm or less, more preferably 30 nm or less.
In some embodiments, the crystalline phase content and refractive index in the microcrystalline glass or microcrystalline glass products of the present invention affect the |B| value of the microcrystalline glass or microcrystalline glass products, and the microcrystalline glass or microcrystalline glass products appear bluish or yellowish when observed in the visible light range, which affects the optical properties of the products, and are marked with |B| value in LAB (chromaticity value of substance color). Microcrystalline glass or microcrystalline glass products present low |B| values in the visible range, and the average light |B| values of microcrystalline glass products or microcrystalline glass 400800 nm in some embodiments with thickness 1 mm or less are 0.9 or less, preferably 0.8 or less, and more preferably 0.7 or less.
In some embodiments, the microcrystalline glass or microcrystalline glass product of the present invention exhibits high transparency in the visible range (i.e., the microcrystalline glass or microcrystalline glass product is transparent). The microcrystalline glass or microcrystalline glass product exhibits high transmittance in the visible range, and in some embodiments, the average light transmittance rate of 400˜800 nm of the microcrystalline glass product or microcrystalline glass of thickness 1 mm or less is preferably 87% or more. In some preferred embodiments, the light transmittance rate at 550 nm of microcrystalline glass product or microcrystalline glass of thickness 1 mm or less is preferably 88% or more.
In some embodiments, an anti-microbial composition may be added to a matrix glass, microcrystalline glass, or microcrystalline glass product. The microcrystalline glass or microcrystalline glass products described herein may be used in applications such as kitchen or restaurant worktops where exposure to harmful bacteria is likely. The matrix glass, microcrystalline glass or microcrystalline glass products contain anti-microbial components including, but not limited to Ag, AgO, Cu, CuO, Cu2O, etc. In some embodiments, the above anti-microbial components are present in amounts of 2% or less, preferably 1% or less, individually or in combination.
The matrix glass, microcrystalline glass and microcrystalline glass products of the present invention can be produced and manufactured by the following methods:
Generate the matrix glass: Mix the raw materials well in proportion to the components, put the homogeneous mixture into a crucible made of platinum or quartz, and melt it in an electric or gas furnace in the temperature range of 1250˜1650° C. for 5˜24 hours depending on the melting ease of the glass composition. After melting and stirring to make it homogeneous, it is lowered to the proper temperature and cast into the mold, which is made by slow cooling.
The matrix glass of the present invention can be molded by well-known methods.
The matrix glass of the present invention is crystallized by a crystallization process after molding or after the molding process to uniformly precipitate crystals within the glass. This crystallization process can be carried out by 1 stage or by 2 stages, and preferably 2 stages are used for the crystallization process. The nucleation process is performed at a 1st temperature, and then the crystal growth process is performed at a 2nd temperature higher than the nucleation process temperature. The crystallization process performed at the 1st temperature is referred to as the 1st crystallization process, and the crystallization process performed at the 2nd temperature is referred to as the 2nd crystallization process.
In order to obtain the desired physical properties of the microcrystalline glass, the preferred crystallization process is:
The above-mentioned crystallization treatment by 1 stage allows the nucleation formation process and the crystallization growth process to be carried out continuously. In other words, the temperature is increased to the specified crystallization temperature, and after reaching the crystallization temperature, the temperature is maintained for a certain period of time, and then the temperature is lowered. The crystallization treatment temperature is preferably 580˜750° C., more preferably 600˜700° C. in order to precipitate the desired crystalline phase, and the holding time at the crystallization treatment temperature is preferably 0˜8 hours, more preferably 1˜6 hours.
When the above crystallization treatment is performed by 2 stages, the 1st temperature is preferably 470˜580° C. and the 2nd temperature is preferably 600˜750° C. The holding time at the 1st temperature is preferably 0˜24 hours, and more preferably 2˜15 hours. The holding time at the 2nd temperature is preferably 0˜10 hours, more preferably 0.5˜6 hours.
The above holding time of 0 hours means that the temperature starts to cool down or warm up again less than 1 minute after reaching that temperature.
In some embodiments, the matrix glass or microcrystalline glass described herein may be manufactured into a shaped body by various processes, the shaped body including, but not limited to, a sheet, and the processes including, but not limited to, slit drawing, floatation, roll pressing, and other processes known in the art for forming sheets. Alternatively, the matrix glass or microcrystalline glass may be formed by float or roll pressing as is well known in the art. The formers described in the present invention also include lenses, prisms, etc.
The matrix glass or microcrystalline glass of the present invention can be manufactured as a glass-forming body or microcrystalline glass-forming body of a sheet by methods such as grinding or polishing processing, but the methods of manufacturing the glass-forming body or microcrystalline glass-forming body are not limited to these methods.
The matrix glass or microcrystalline glass of the present invention can be prepared to form various shapes of glass-forming bodies or microcrystalline glass-forming bodies at a certain temperature using methods such as hot bending process or press molding process, but is not limited to these methods.
In some embodiments, a glass forming body or microcrystalline glass forming body can be made using a heat bending process. The heat bending process is a process in which 2D or 2.5D glass or microcrystalline glass is placed in a mold and a 3D curved glass forming body or microcrystalline glass forming body is made in a heat bending machine in a sequence of steps including heating up and preheating, pressurizing and forming, and holding pressure and cooling.
In some embodiments, the microcrystalline glass forming body has a 2.5D or 3D configuration, i.e., the microcrystalline glass forming body has a non-planar configuration. By “non-planar configuration” as used herein, we mean that in a 2.5D or 3D shape, at least a portion of the microcrystalline glass forming body extends outward or along an angle with a plane defined by the original, layout configuration of the 2D matrix glass. The 2.5D or 3D microcrystalline glass forming body formed from the matrix glass may have one or more projections or curved portions.
In some embodiments, the method of manufacturing the microcrystalline glass forming body is a heat bending process method in combination with the characteristics of the growth and transformation of the crystalline phase in the microcrystalline glass. Specifically, the method includes pre-crystallization and hot process forming. The pre-crystallization described in the present invention is to form a pre-crystallized glass from a matrix glass (i.e., glass before crystallization) by a controlled crystallization process. The crystallinity of the pre-crystallized glass does not reach the crystallinity required for the performance index of the target microcrystalline glass forming body. The pre-crystallized glass is then formed into a microcrystalline glass forming body by a thermal processing molding process.
In some embodiments, the method of manufacturing a microcrystalline glass forming body comprises the steps of:
The crystallization heat treatment process described in the present invention consists of nucleation of the matrix glass at a certain temperature Th and time th, followed by crystallization at a certain temperature Tc and time tc. The crystallinity of the obtained pre-crystallized glass does not reach the crystallinity required for the performance index of the target microcrystalline glass forming body. Applying the XRD test data, the total content of the main crystalline phase in the crystallinity of the pre-crystallized glass was calculated by the Rietveld full-spectrum fitting refinement method as Ic1. The pre-crystallization of the present invention is a complete process in terms of process, including one step of the nucleation process, one, two or three and more stages of the crystallization process, etc. It is a complete process from heating and holding, and again heating and holding . . . , and then to room temperature according to the process. Distinguished from the primary crystallization and secondary crystallization mentioned in some literature or patents . . . , the present invention is actually only the first stage of a complete crystallization process, and the second stage of the crystallization. It is continuous, and there is no process of crystallization by lowering to room temperature and then raising the temperature again.
The thermal processing molding described in the present invention refers to the molding treatment of pre-crystallized glass by thermal processing process under certain conditions of temperature, time, pressure, etc. The thermal processing molding includes more than one thermal processing process, and the thermal processing process includes but is not limited to pressing molding, bending molding or drawing molding of pre-crystallized glass under certain conditions of temperature, time, pressure, etc. In the thermal processing molding process, sometimes the complex shape of the molding body cannot be completed by one thermal processing, and it may be necessary to perform more than two multiple thermal processing to achieve.
In some embodiments, the method of manufacturing the microcrystalline glass forming body is a heat bending process method. Specifically, in some embodiments, the method of manufacturing the microcrystalline glass forming body comprises the steps of:
Microcrystalline glass forming body using heat bending process not only needs to control the appearance quality such as ordinary high alumina glass, but also needs to control the influence of crystal growth and development on the performance of microcrystalline glass during the heat bending process, such as 3D curved microcrystalline glass used for display devices or electronic equipment housing, which needs to pay close attention to the light transmittance, haze, |B| value and its uniformity after heat bending.
In some embodiments, the primary crystalline phase of the pre-crystallized glass contains lithium monosilicate, and/or lithium disilicate, and/or lithium phosphate, and/or quartz solid solution and/or petalite, the rang of crystalline phase content is 20˜60%, wherein the petalite content is 0˜18%. The main crystalline phase of the microcrystalline glass forming body formed by the hot bending process contains lithium disilicate, or lithium disilicate and petalite, the rang of crystalline phase content is 40˜70%, where the petalite content is 0˜18%.
In some embodiments, the primary crystalline phase of the pre-crystallized glass contains lithium monosilicate, and/or lithium disilicate, and/or lithium phosphate, and/or quartz solid solution, and/or petalite, the rang of crystalline phase content is 20˜60%, where the petalite content is 0˜18%. The main crystalline phase of the microcrystalline glass forming body formed by the hot bending process contains lithium monosilicate and/or lithium disilicate, the rang of crystalline phase content is 40˜70%.
The amount of change of crystalline phase before and after heat bending determines the uniformity of microcrystalline glass forming body in terms of size, mass production possibility and cost control, etc. The matrix glass and microcrystalline glass of the present invention have excellent thermal processing properties, and the amount of change of crystalline phase content is 20% or less, preferably 15% or less, and further preferably 10% or less after heat bending and molding, which can ensure the uniformity of haze and |B| values, etc. of microcrystalline glass forming body obtained after heat bending.
The matrix glass, microcrystalline glass and microcrystalline glass products described herein may have any thickness that is reasonably useful.
The microcrystalline glass of the present invention can improve mechanical properties through precipitation crystallization, and in addition to obtaining superior mechanical properties by forming compressive stress layers to be made into microcrystalline glass products.
In some embodiments, the matrix glass or microcrystalline glass can be processed into sheets, and/or shaped (e.g., perforated, heat bent, etc.), polished and/or swept after shaped, and then chemically strengthened by a chemical strengthening process.
The chemical strengthening described in this invention is the ion exchange method. In the ion exchange process, smaller metal ions in the matrix glass or microcrystalline glass are replaced or “exchanged” by larger metal ions with the same valence state close to the matrix glass or microcrystalline glass. The replacement of smaller ions with larger ions builds compressive stress in the matrix glass or microcrystalline glass, forming a compressive stress layer.
In some embodiments, the metal ions are monovalent alkali metal ions (e.g., Na+, K+, Rb+, Cs+, etc.), and the ion exchange is performed by submerging the matrix glass or microcrystalline glass in a salt bath containing at least one molten salt of a larger metal ion that is used to displace the smaller metal ion in the matrix glass. Alternatively, other monovalent metal ions such as Ag+, Tl+, Cu+, etc. can be used to exchange monovalent ions. One or more ion exchange processes used to chemically strengthen the matrix glass or microcrystalline glass may include, but are not limited to, submerging it in a single salt bath or submerging it in a plurality of salt baths having the same or different compositions, with washing and/or annealing steps between submersions.
In some embodiments, the matrix glass or microcrystalline glass may be ion-exchanged by submersion in a salt bath of molten Na salt (e.g., NaNO3) at a temperature of about 350˜470° C. for about 1˜36 hours, preferably in the temperature range of 380˜460° C. and preferably in the time range of 2˜24 hours. In this embodiment, the Na ions replace some of the Li ions in the matrix glass or microcrystalline glass to form a surface compressed layer and exhibit high mechanical properties. In some embodiments, the matrix glass or microcrystalline glass can be ion exchanged by submerging in a salt bath of molten K salt (e.g., KNO3) at a temperature of about 360˜450° C. for 1˜36 hours, preferably in the time range of 2˜24 hours. In some embodiments, the matrix glass or microcrystalline glass may be subjected to ion exchange by submersion in a mixed salt bath of molten K and Na salts at a temperature of about 360˜450° C. for 1˜36 hours, preferably in the time range of 2˜24 hours.
Each performance index of microcrystalline glass and/or microcrystalline glass products and/or matrix glass of the present invention is tested by the following methods:
[Haze]
Using Minolta CM3600A, a haze tester, samples of 1 mm or less were prepared and tested according to GB2410-80.
[Grain Size]
Determination was performed using SEM scanning electron microscopy. The microcrystalline glass was surface treated in HF acid and then gold sprayed on the surface of the microcrystalline glass, and the size of the grains was determined by surface scanning under SEM scanning electron microscopy.
[Light Transmittance Rate]
The light transmission rates described in this paper are all external transmission rates, sometimes referred to as transmission rates.
The samples were processed to 1 mm or less and polished parallel to each other, and the average light transmittance from 400 to 800 nm was measured using a Hitachi U-41000 shaped spectrophotometer.
The samples were processed to 1 mm or less and polished parallel to each other, and the light transmittance at 550 nm was measured using a Hitachi U-41000 shaped spectrophotometer.
[Crystallinity]
The XRD diffraction peaks were compared with database profiles, and the crystallinity was obtained by calculating the proportion of the crystalline phase diffraction intensity in the overall profile intensity and by internal calibration using pure quartz crystals.
[Ion Exchange Layer Depth]
The ion-exchange layer depth was measured using a glass surface stress meter SLP-2000.
The refractive index of the sample was 1.56 and the optical elasticity constant was 26 [(nm/cm)/Mpa] as the measurement conditions.
[Falling Ball Test Height]
A sample of 145 mm×67 mm×0.7 mm microcrystalline glass product is placed on a glass-bearing fixture, and a 132 g steel ball is dropped from a specified height, and the sample is subjected to the maximum drop test height of impact without fracture. Specifically, the test is implemented from the ball drop test height of 800 mm, without fracture, through 850 mm, 900 mm, 950 mm, 1000 mm and above in order to change the height. For the example with “ball drop test height”, the test object is a microcrystalline glass product. In this case, the test data of 1000 mm is recorded, which means that even if a steel ball is dropped from a height of 1000 mm, the microcrystalline glass product does not break and withstands the impact. The height of the ball drop test in this invention is sometimes referred to as the height of the ball drop.
[Drop Height of the Body]
The 145 mm×67 mm×0.7 mm microcrystalline glass sample is placed on the glass-bearing fixture, so that a 32 g steel ball is dropped from a specified height, and the maximum drop test height of the sample that can withstand the impact without fracture is the drop height of the body. Specifically, the test is implemented from the ball drop test height of 500 mm, without fracture, through 550 mm, 600 mm, 650 mm, 700 mm and above to change the height in turn. In the case of the embodiment with the “body drop height”, the drop height of microcrystalline glass is used as the test object, which is the drop test height of microcrystalline glass. In the case of the test data recorded as 1000 mm, it means that even if the steel ball is dropped from a height of 1000 mm, the microcrystalline glass does not break and withstands the impact.
[Fracture Toughness]
Using the method of direct measurement of indentation extended crack size, the specimen size was 2 mm×4 mm×20 mm, chamfered, smoothed and polished, and after the specimen preparation, a force of 49N was applied to the specimen with a Vickers hardness indenter and maintained for 30 s, and the fracture strength was determined by three-point bending method after punching out the indentation.
[Four-Point Bending Strength]
A microcomputer-controlled electronic universal testing machine, CMT6502, with sample specifications of 1 mm thickness or less, was used to perform the test in accordance with ASTM C 158-2002. The four-point bending strength is sometimes referred to as bending strength in this invention.
[Vickers Hardness]
The value expressed by dividing the load (N) when pressing a pyramid-shaped depression into the test surface with a diamond quadrilateral cone indenter with an angle of 136° on the relative surface by the surface area (mm2) calculated through the length of the depression. Make a test load of 100 (N) and a holding time of 15 (sec) to carry out. The Vickers hardness is sometimes referred to as hardness in the present invention.
[|B| Value]
B-value testing was performed using Minolta CM-700d. The sample size is below 1 mm thickness, use the supporting calibration long cylinder and short cylinder for instrument zero calibration and whiteboard calibration respectively, after calibration, use the long cylinder and then carry out the test against the empty space to determine the instrument stable calibration reliability (130.05), after the instrument calibration is qualified, place the product on the long cylinder at zero position for testing.
The value of |B| is the absolute value of the value of B.
[Coefficient of Thermal Expansion]
Thermal expansion coefficient (α20° C.-120° C.) tested according to GB/T7962.16-2010 test method.
[Refractive Index]
Refractive index (nd) tested according to GB/T7962.1-2010 method.
[Dielectric Constant]
Dielectric constant (εr) in accordance with GB 9622.9-1988 method test, test frequency of 1˜7 GHZ.
[Dielectric Loss]
Dielectric loss (tan δ) in accordance with GB 9622.9-1988 method test, test frequency of 1˜7 GHZ.
[Surface Resistance]
The surface resistance is tested according to CS-157-2020 method, and the test temperature is 20˜40° C.
The microcrystalline glass products of the present invention have the following properties:
The microcrystalline glass of the present invention has the following properties:
The matrix glass of the present invention has the following properties:
The microcrystalline glass, microcrystalline glass products, matrix glass, glass forming body, microcrystalline glass forming body of the present invention can be widely made into glass cover or glass components due to the above-mentioned excellent properties; meanwhile, the microcrystalline glass, microcrystalline glass products, matrix glass, glass forming body, microcrystalline glass forming body of the present invention can be applied in electronic devices or display devices, such as cell phones, watches, computers, touch screens, etc., for manufacturing protective glass for cell phones, smart phones, tablet PCs, laptops, PDAs, televisions, personal computers, MTA machines or industrial displays, or for manufacturing touch screens, protective windows, car windows, train windows, aviation machinery windows, protective glass for touch screens, or for manufacturing hard disk substrates or solar cell substrates, or for manufacturing white goods, such as for manufacturing refrigerator parts or kitchenware.
In order to further clearly illustrate and describe the technical embodiments of the present invention, the following non-limiting embodiments are provided. Many efforts have been made to ensure the accuracy of the values (e.g., quantity, temperature, etc.) for embodiments of the present invention, but it must be taken into account that some errors and biases exist. The composition itself is given in weight % based on the oxide and has been normalized to 100%.
In this embodiment, the matrix glass having the compositions shown in Tables 1˜6 was obtained by the manufacturing method of the matrix glass described above. In addition, the characteristics of each matrix glass were measured by the test method described in the present invention, and the measurement results are expressed in Tables 1˜6.
In this embodiment, the microcrystalline glass having the compositions shown in Tables 7˜12 was obtained by the manufacturing method of microcrystalline glass described above. In addition, the characteristics of each microcrystalline glass were measured by the test method described in the present invention, and the measurement results are expressed in Tables 7˜12 for the room temperature described in the following embodiments, i.e., 25° C.
In this embodiment, the microcrystalline glass products having the compositions shown in Tables 13˜18 were obtained using the manufacturing method of the microcrystalline glass products described above. In addition, the characteristics of each microcrystalline glass product were measured by the test method described in the present invention, and the measurement results are expressed in Tables 13˜18.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202110116889.X | Jan 2021 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2022/070074 | 1/4/2022 | WO |
