JPH01103928A - Reformed oxynitride glass and production thereof - Google Patents

Abstract

PURPOSE:To form high quality oxynitride glass having a much higher nitrogen content than conventional glass, high hardness and elasticity by specifying the mixing ratios in the compsn. of oxynitride glass. CONSTITUTION:The amts. (mol.%) of SiO2, Si3N4 and M1O in Si-M1-M2-O-N type oxynitride glass (M1 is Ca or Ca+Mg and M2 is a metal other than Ca and Mg) are allowed to satisfy inequalities 65<=(SiO2+3Si3N4+M1O)X100/(100+2 Si3N4)<100 and 0.7<=(SiO2+3Si3N4)/M1O<=2.3. The glass contains 10-24atom.% Ca+Mg (Canot equal to 0% and Mg=0%) and >=15atom.% nitrogen element.

Description

DETAILED DESCRIPTION OF THE INVENTION G) Industrial Application Field This invention provides high quality oxynite wide glass which has higher hardness and greater elasticity than previously known by containing 15 at% or more of nitrogen. This article relates to a method for producing glass fibers or chips, which can be used as reinforcing agents for plastic compositions, for lining the surfaces of metal casings, and as leaf materials for composite materials.99. Furthermore, it can be widely used in various fields, such as making hard, high tensile strength molded products in plate or bulk form.

(01 Prior Art Oxynitride glass has a structure in which the oxygen atoms of ceremonial glass are replaced with nitrogen.

Since the bond valence of nitrogen atoms is 3, it has a higher elastic modulus than conventional glasses.

As conventional J-xynitride glass.

Ca-Si-aJ-o-N, Na-Ca-8
i-0-N.

La -8i -kl knee 0-N, Na -B -8
i-Q-N.

Mg -8i -Al-0-N, Si -u -0-
N.

Y-AI! -8i -0-N, Na -B -J-
Some have compositions such as P-0-N.

In order to obtain oxynitride glass with such a composition, there is a melting method in which metal nitride is added to metal oxide and melted at high temperature, and an oxide glass precursor with -OH or -0Rt- and N
A sol/gel method using Hs reaction is known.

Here, examples of metal oxides include '5iOz, Na
zO.

K2O, La2.3. Cab, Y2O3, ZrO2, T
i0z, Na2O, 20°B2O3, etc.; examples of metal nitrides include 8isN4*Aδ; and examples of oxide glass precursors with -OH or -OR include silicon tetrafalkoxide, titanium, Examples include tetraapkoxide.

As mentioned above, oxynitride glasses containing various elements have been known, but in all of them, the nitrogen content has only reached about 7 to gat%. According to the present invention, no material containing nitrogen at a high concentration of 15 at % or more has been known so far. This is because conventionally known additives and their blending ratios do not sufficiently replace the oxygen element in the oxide with nitrogen, resulting in a glass with a low nitrogen concentration. It's a good thing and a good friend.

Therefore, the problem with this suppressed oxynitride glass is how to increase the efficiency of nitrogen substitution, and there is no known example in which this problem has been solved in one go.

B) Means for Solving the Problems In view of the above, the present invention has been developed by adding oxidizing power p-sium (CaO) or thermal decomposition to an oxynitride galanic raw material consisting of silicic acid, metal oxides, and metal nitrides such as silicon nitride. By adding a larger amount of Ca salts, which become CaO than previously thought, and by limiting the mixing ratio of calcium oxide to silicic acid and nitride within a specific range, the oxygen element in the oxide can be reduced. It was discovered that the nitrogen substitution efficiency of the glass was significantly improved, and as a result, the nitrogen content in the glass after melt forming could be increased to t-15 at% or more, resulting in a high hardness and hardness that could not be obtained with conventional glass. The first invention is an invention of the composition itself of the oxynitride wide glass obtained as described above.

In the manufactured glass, Ca primary is (Ca −f
-Mg) is contained in the range of 10 to 24 at%, and the nitrogen content is 15 at% or more. Here Ca
If (Ca + Mg) is less than 10 at%, the glass will have a low nitrogen content! As a result of experiments, it was confirmed that if it exceeds +24 at%, it will not crystallize and become glassy.

In addition, glass raw material (SiO
z, 8i3Ni, Ca0 or CaO+MgO)
Expressed in terms of k mixing ratio, it is as follows (aJ, Lb1 formula % formula % (0 friends expressed as 100, MlμCa'!fc indicates Ca and Mg, 8i0z, 5isN4.
The number expressed as (using direct).

The third invention is a method for manufacturing glass having such a composition.

The present invention is based on 5in2.8i3N< and a nitride selected from the group of metal nitrides, CaO (CaO-1-Mg
O) Ca0 (CaO + Mg0) due to thermal decomposition
Ca salt (Ca salt + Mg salt).

Metal oxides other than CaO and MgO (expressed as 1 mol% of glass raw material consisting of λ containing salts that become metal oxides by thermal decomposition), Ca
b. MgO is mixed so as to satisfy the following formula % (%), and the mixture is heated and melted at a temperature of 1400 to 1900°C in an inert gas atmosphere.

Examples of gold jimides other than Cab and MgO include 9, 8
rO.

ZrO2+ T iOz, M2O3,, Y2O31L
a2'3. CeO2, Bad, Na 20,820
At least 1#11 metal oxides selected from 3, etc. are used. ′! Friend, this metal oxide is a metal salt (it may be a substance that can be carbonated) that becomes the metal oxide by thermal decomposition.Also, as a metal nitride other than 5r3Na, when using M2O3 as the metal oxide, IN is , RN is effective when using R2O3.

Note that if the formula (b) is not within the above range, the nitrogen content will not increase and a highly elastic glass will not be obtained, and if the formula (b) is outside the above range, crystallization will occur and a glass state will not be obtained. It was found from the experiment.

The melting temperature may be within the range of 1400 to 1900°C at which the mixture of the metal oxide and metal nitride melts, and the mixture does not melt at temperatures below this range.

Temperatures above this range will cause the mixture to burn. Melting is performed in a heating furnace such as an electric furnace or an image furnace. By heating and melting in this way, it is more effective than the sol-gel method.

Improve the rate of nitrogen substitution of oxygen elements in oxides.

The nitrogen content in melt-formed glasses can be significantly increased.

According to the present invention, by specifying the mixing ratio of the composition of oxynitride glass, the efficiency of nitrogen replacement of oxygen elements in the oxide of the glass composition is significantly improved, and the nitrogen content in the glass is reduced. (I-15 at% or more. As a result, the 91 surface has a denser network structure than conventional glass due to the high degree of crosslinking due to 84-N bonds, and has high hardness and high elasticity. A glass having the following characteristics is obtained.

(f) Example 5 Fifty-three samples of glass raw materials of various compositions containing iOz, metal oxides, and metal nitrides as main components were prepared as shown in Table 1, and all of them were heated and melted to produce glass. Its nitrogen content, hardness, and elastic modulus were measured.

However, Samples 1 to 44 in Table 1 are obtained by blending each raw material in the composition ratio of the present invention, and Samples 45 to 53 are samples for comparison.

Specific experimental examples and comparative examples for the four representative samples in Table 1 are shown below.

Experimental example 1 Raw material of sample example 1 in Table 1, namely 8i0z26mo%,
8isN411molA/, CaO52,4molL/
Ip6. A raw material powder consisting of MgO 5 mo μ% * AZ zOs 4-6 mo/L'% was thoroughly mixed, and this was pressure-molded using a rolling roller at 1500 My-A:d for 30 seconds to form a solid shape. This was placed in an image furnace and heated for 3 minutes in a nitrogen gas atmosphere to 1730°C to melt it. Next, it was rapidly cooled by twin rollers to produce glass.

The obtained glass was in the form of flakes with a thickness of 25 μm.

The nitrogen content of this glass was measured by the Kaeder μ method and was found to be 15.28 t%.

In addition, as a result of measuring the hardness and elastic modulus of this glass flake, 959 Kl-Ml-2 and 14000KP-
'181-2.

Comparative Example 1 In the same manner as in Experimental Example 1, the raw materials of Sample Example 51 in Table 1, i.e., 5if265 moA/%, 8i3N45.0
Molv%.

Ca010 mol%-At! A glass was created based on a raw material consisting of zOs 20.0 moN96.

The nitrogen content of the obtained glass was 5. lat%, hardness 68
0MP-Female-29 Elastic modulus 11100 KVIII-”
Met.

This is it (S i02+ 381sN4)/ (!
'ao is not within the range of the present invention, the nitrogen content is 15at
% or higher hardness and high elastic modulus could not be obtained.

Experimental example 2 Raw material of sample example 19 in Table 1, namely 5i0236.1 mo, v%, 8 r 5N48.5 moi'5'lS @
Ca030.7 μ%.

Mg83.0moμ%, Aj'zOs 7.8mo/L/
%, AJN 13.9 μ% was heated and melted in the same manner as in Experimental Example 1. Next, glass was created by dropping this onto an iron plate placed under the furnace.

The created glass has a nitrogen content of 15.7 at% and a hardness of 7.
99 g, 5+-a-2, elastic modulus 12.600 El!
・It was wf2. This also revealed that A7N is effective as a nitriding source.

Experimental Example 3 Raw material of Sample Example 43 in Table 1, namely 8i027.5Mo
%* 5isN421.3mol%, Ca066.7mol%, Mg82.9mol%, ki2es 31.6
Air
After premelting at 1450 to 1500° C. and pulverizing, this was mixed with a nitride raw material (8isN4). This mixture iB
The mixture was placed in a N ~ crucible and melted at 1790''O in a nitrogen gas atmosphere, and after 30 minutes, the power to the furnace was turned off, and the glass was warmed and cooled to room temperature.

The glass created in this way has a nitrogen content of 26.7 at.
%, hardness 1210Kg-1f” elastic modulus 23700fl
It was y-wx-2.

In addition, sample examples 2.3.7 to 18.20 to 42 in Table 1
Nitrogen content, Ca+Mg content, Vickers hardness 9 elasticity modulus when Samples 4 to 6 were carried out using the method of Experimental Example 3, Samples 4 to 6 were carried out using the method of Experimental Example 1, and Sample Example 44 was carried out using the method of Experimental Example 1. It is shown in the lower column of IT Table 10.

Idgaras was not obtained.

That is, (5iOz+38iiN4+M+O)
Sump/L' 45, 46 where 100/(100+28iOz) is less than 65 is partially crystallized and pure glass cannot be obtained, and (8i02 +38iiN4)/M
In the sample/l/47.48 where tO is less than 017, the raw material does not melt and becomes crystal p (SiO2+38isN4)
Sample 49.50 with 7M1o exceeding 2.3 was molten but contained some crystalline phase.

Furthermore, when the sample for comparative example/1152,53i was processed using the method of Experimental Example 3, glass was obtained, but it was a glass with low hardness and low modulus of elasticity. Figure 1 shows the relationship between nitrogen content and Vickers hardness of the glass produced. This figure shows that when the nitrogen content is 15 at % or more, the hardness increases and a glass with high hardness can be obtained.

Furthermore, FIG. 2 shows the relationship between the nitrogen content and the elastic modulus of glasses produced by the same method. In this figure, the nitrogen content is also 1.
It can be seen that when the content is 5 at% or more, the elastic modulus increases and a high-performance glass can be obtained.

(g) Effects According to the present invention, the nitrogen content 1, which could not be achieved conventionally,
5 at% or more glass can be achieved, therefore.

A glass with unprecedented high hardness and high elasticity was obtained.

[Brief explanation of the drawing]

Figure 1 shows the relationship between the nitrogen content and Vickers hardness of the glass produced by the method of Experimental Example 1, and Figure 2 shows the relationship between the nitrogen content and elastic modulus of the glass produced by the method of Experimental Example 1. FIG. Figure 1: V cord content (at@) Figure 2: Mushroom mushroom t (at%)

Claims (1)

[Claims] 1. An oxynitride glass obtained by substituting a part of the oxygen element in the oxide of a silicic acid and metal oxide glass with a nitrogen element, in which (Ca+Mg) is 1.
A modified oxynitride glass characterized by containing 0 to 24 at% of nitrogen element and having a nitrogen element content of 15 at% or more. (However, if Ca≠0, Mg
= 0) 2. In oxynitride glass consisting of Si-M_1-M_2-O-N system, SiO_ expressed in mol%
2. Si_3N_4, M_1O are as follows (a), (b) formula 65≦(SiO_2+3Si_3N_4+M_1O)×
100/(100+2Si_3N_4)<100...
(a) 0.7≦(SiO_2+3Si_3N_4)/M_1O
A modified oxynitride glass characterized by satisfying ≦2.3 (b). (However, M_1 indicates Ca or Ca and Mg, M_2 indicates a metal other than Ca or Mg.) 3. SiO_2, Si_3N_4 and a nitride selected from the metal nitride group, CaO (CaO + MgO) or CaO (CaO + MgO) by thermal decomposition. ) is the Ca salt (
Ca salt + Mg salt), CaO and metal oxides other than MgO (including salts that become metal oxides by thermal decomposition) are added to the glass raw material consisting of SiO_2, Si_3 expressed in mol%.
N_4, CaO, and MgO using the following formulas (a) and (b) 65≦(
SiO_2+3Si_3N_4+CaO+MgO)×1
00/(100+2Si_3N_4)<100...
...(a) 0.7≦(SiO_2+3Si_3N_4)/(CaO
+MgO)≦2.3...(b) The mixture is heated and melted at a temperature of 1400 to 1900°C in an inert gas atmosphere. Manufacturing method. (However, in equations (a) and (b), CaO≠0 and MgO=
(including 0)