JPH01122937A - Frit for glass flame spraying - Google Patents

Abstract

PURPOSE:To supply frit capable of being readily subjected to flame spraying, containing no lead component, by specifying a composition comprising SiO2, Na2O, K2O and B2O3 as essential components. CONSTITUTION:This frit for glass flame spraying comprising 35-70wt.% SiO2, 5-20wt.% Na2O, 0.1-10wt.% K2O, 10-35wt.% B2O3, 0-10wt.% Al2O3, 0-15wt.% Li2O, 0-10wt.% CaO, 0-15wt.% F2 substituted amount and 0-20wt.% one or more of TiO2, ZnO, ZrO2, SnO2, SrO, MgO, MoO3, BaO, P2O5, Sb2O5, CeO2, V2O5 and Bi2O3 as an additive. Glass flame spraying which has been considered to be difficult can be extremely readily carried out by using the frit and problems with respect to health and pollution can be avoided since no lead component is contained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a frit for glass thermal spraying, and particularly to a frit that does not contain a lead component and can be easily thermally sprayed.

(Background of the Invention) For example, as disclosed in Japanese Unexamined Patent Application Publication No. 60-235775, it is possible to spray glass to form a glass coating on the surface of an object to be coated, such as a full bend or cement. Frits are useful as thermal spray materials.

However, the reality is that no matter what kind of frit is loaded into the thermal spraying equipment, a glass coating is never easily formed, and in some cases, the frit is not melted at all and is discharged from the thermal spraying equipment in its powder form. Sometimes. Generally 2500 to 3200℃ in thermal spray equipment
Although it is possible to raise the temperature to a certain degree, a certain amount of time is required for the frit to melt into a glassy state. However, since material is discharged at an instantaneous speed in thermal spraying equipment, the frit material must be compatible with such properties.

Furthermore, harmful lead components must be avoided as much as possible due to health and pollution problems.

(Problems to be Solved by the Invention) This invention was proposed in the above situation, and it is a method of forming a glass coating on the surface of metals such as iron, stainless steel, and cast iron, or of objects to be coated such as cement. Particularly, it is an object of the present invention to provide a frit that can be quickly melted in the flame of a thermal spraying device. That is. Another object of the present invention is to provide a frit for glass thermal spraying that does not contain lead components.

(Means for Solving the Problems) That is, the glass thermal spray frit according to the present invention contains Sio2 35-70% Na2O5-2 at least in weight%.
0% K2O 0.1-10% B2O3 10-35% A text 203 0-1O% Li2o 0N15% CaOO-10% F2 substitution amount 0-15% Contains TiO2, ZnO as additives.

ZrO2, SnO, , SrO, MgO, MoO3.

Ba02P205.5b205, ceo2, v20
5. 0 to 20 of one or more types of Bi2O3
%.

(Function) Next, the function of each composition will be explained in detail. SiO2 is a main frit-forming oxide and has a large influence on the coefficient of thermal expansion, softening point, and wear resistance. This 5i02 is 3
The reason why it is set at 5 to 70% is that the higher the amount of 5102, the higher the abrasion resistance, weather resistance, and acid resistance, and the better the performance of the glass film. However, if the amount is too large, the refractoriness of the frit will be high and the spraying temperature will have to be increased, and therefore the preheating temperature of the object to be coated will also have to be increased.

The reason why B2O3 is set to 10 to 35% is based on the reason that if the content is too high, the abrasion resistance, weather resistance, and acidity will deteriorate, but if the content is -, the frit refractoriness will be lowered.

Due to the relationship with other components in the present invention, if it is less than 105, the melting point of the frit itself becomes high;
If it exceeds %, hot water resistance, #climate resistance, and acid resistance will deteriorate. B
When the amount of 2O3 is increased, melting occurs quickly in the flame of the thermal spraying device. Furthermore, when alkali is added to this B2O3, the 8 expansion coefficient gradually decreases, and Na
By adding 20% in the range of 5 to 20%, it becomes minimum.

An, 03 is a frit formation auxiliary component and improves the performance of the glass film, but if it exceeds 10%, the melting temperature of the frit increases.

K2O is a type of alkaline compound and is an important component for lowering the melting point, but when the amount is large, weather resistance deteriorates.

Adding LL20 increases the electrical resistance of the product.

This is also to increase hardness and improve chemical durability.

Furthermore, when a large amount of S i 02 is present, it is blended in a range of 0 to 15% in order to increase the expansion coefficient of the frit.

And, blending 0-15% of F2 substitution amount is F2
This is because when B2O3 enters, the fire resistance decreases due to the mutual effect with B2O3, and the work performance of thermal spraying increases.

F is CaF or Na2S iF2, Na5AnF
It is often used in the form of B.

In addition, the total amount of NaO+K2O+B2O3 is 1O to 5
A range of 0% is desirable in order to facilitate glass spraying using this type of printing.

Within this range, the frit will melt quickly within the flame of the thermal spraying device. If the total amount of these is less than 10%, the melting temperature will be high and it will be necessary to increase the preheating temperature during thermal spraying, and the surface will not be smooth. If it exceeds 50%, the wear resistance will be poor due to the relationship with other components. This is because weather resistance, acid resistance, and heat resistance are significantly reduced.

As mentioned above, when the amount of S t 02 increases, the properties of the glass film, ie, abrasion resistance, weather resistance, chemical resistance, etc., improve. However, when SiO2 increases, 7
The coefficient of expansion of the lift becomes small, resulting in a large difference from the coefficient of expansion of the object to be coated, such as metal.

Therefore, in such a case, N a O, L s 2
By increasing the amount of 0, CaO, etc., the expansion coefficient of the frit is increased to match the expansion coefficient of the object to be coated. In addition,
If the expansion coefficients of the object to be coated do not match, a part of the thermally sprayed diameter coating will fly off or become weak against impact, and it will be difficult to form a coating with a thickness on the order of am.

Furthermore, as the amount of SiO2 increases, the refractory strength of the frit increases, making it necessary to increase the thermal spraying temperature and the preheating temperature of the object to be coated. However, for example, when the object to be coated is iron, the thermal variation point of iron is 723°C, so it is preferable to preheat the temperature below this thermal variation point. To enable the formation of additives such as CaO, TsO, ZnO, Z
r O2, Sn O2, S r O, M g O, M
o O3, B a O, P2O5, Sb205,
One or more of CEO, V, , O5, Bi2O3 is added in an amount of 0 to 20%.

These additives facilitate rapid melting of the frit during thermal spraying. Note that in cases where the preheating temperature of the material to be coated can be high (800° C. or higher), such as stainless steel, these additives may be unnecessary.

Also, CaO, Tt02, ZrO2, ZnO, Sn
O2, M g O, B a O-P 205, etc. can improve film performance such as weather resistance and acid resistance depending on the amount added.

(Example) Next, an example will be described using a case where glass spraying is performed on a steel plate as an example.

[Frit component example 11 (all % by weight) S i
O2 41% Na, 0 12% K2O 2 , 5% B2O 3 24% A, 03 6.5% Li 20 3 , 4% CaO2, 1% T io 2 1% ZnO 1% ZrO2l % S no 21 , 5% F2 substitution Amount 4% [Frit component example 2] (All weight%) S io
2. 51% N a20 10% K2O 2% B2O3 21% A203 3% Li20 2% CaO1% T i O21% ZnO1% Z r 02 1% S n 02 1% Mo 0 1% F2F2 substitution amount 4% [ frit Component Example 3] (all % by weight) SiO
262% Na20 7, 5% K2O 1% B2O3 17% Adan 203 1% L 120 1% CaO1% T 102 1% Zn0 1% ZrO21% S n 02 1% Mo 0 1% F Substitution amount 3.5% BaO1% [Frit component example 4] (All weight%) S r
02 55% Na 20 9% K2O 1% B2O3 18% A sentence, 03 1% Li20 2% CaO1% 7102 1% ZnO1% Z r O21% S n 02 2% F2 equipment amount 4% BaO1% Bl 20 3 1 % SrO1% 5b20. 1% [Frit component example 5] (All weight%) S I
O255% Na2O10% K2Ol % B2O318% A text 203 1% L 120 1% CaOl % 7102 1% Zn0 1% ZrO21% Sn O22% F2 substitution amount 4% Ce O22% V2O52% [Frit Ingredient example 6] ( Both gL amount%)S i
O268% Na 20 6% K2O l % B203 14% A 0 0.5% L 120 0, 9% CaO0,9% TiO20, 9% ZnOO, 9% ZrO20, 9% S n 02 0, 9 5 M o O0, 8% F2F2 substitution amount 3.5% BaOO, 8% The frit consisting of the above formulation was loaded into an oxyacetylene thermal spraying device, and sprayed onto the surface of an iron plate preheated to 300 to 700°C to obtain a coating composition of 0.05%. A glass coating with a thickness of ~5 cm was obtained. Note that it is preferable that the surface of the iron plate be subjected to sand or shot blasting treatment in advance.

According to the frit of the above example, an extremely good glass coating could be formed on the surface of the object to be coated which had been preheated to 300 to 700°C. The fluidity of the frit was good and there were almost no cracks after thermal spraying.

In addition, when applying an appropriate color to the glass, a desired amount of known pigments are mixed. Pigments include CoO, NiO, M
nO2, Cub, Fe2O3.

CrO, 5n02, TiO2, V2O5, Nbo
, Zr5iO, MoO, WO, Pr203, Nd2O
3, etc., or in the form of a compound (for example, about 5%).

Furthermore, in all of the above component examples, the preheating temperature of the object to be coated is 70
In the case where the preheating temperature is set to 0° C. or lower, if the preheating temperature can be made considerably high, F2 and additives can be made unnecessary as shown in the following component example 7 or 8.

[Frit component example 7] (All weight %) S r
02 55% Na20 12% K2O 3% B2O320% L + 20 2% F Calibration 8% [Frit component example 8] (All weight%) SiO
255% Na20 14% to 2o3% B2O324% L + 202% T t O21% ZrO21% (Effects) As explained above, according to the present invention, glass spraying, which was conventionally thought to be difficult, can be achieved. It has been possible to provide a frit that is extremely easy to perform, and has brought great benefits to this field of technology. Further, according to the present invention, since it does not contain a lead component, health and pollution problems can be avoided, and an extremely practical and highly practical frit for glass thermal spraying can be provided.

Claims (1)

[Claims] Contains at least in weight percent SiO_235-70%, Na_2O5-20%, K_2O0.1-10%, B_2O_310-35%, Al_2O_30-10%, Li_2O_0-15%, CaO0-10%, F_2 substitution amount 0-15%, and TiO_2, ZnO, Zr as additives
O_2, SnO_2, SrO, MgO, MoO_3, B
aO, P_2O_5, Sb_2O_5, CeO_2, V
A frit for glass thermal spraying characterized by containing 0 to 20% of one or more of _2O_5 and Bi_2O_3.