CN106957149A - Frit for porcelain enamel - Google Patents

Abstract

The invention discloses a kind of frit for porcelain enamel, by weight percentage, it is made up of following components：SiO₂50~65%, Al₂O₃20~30%, B₂O₃4~15%, Na₂O 1.2~1.5%, K₂O 1.3~1.6%, CeO₂1~10%, CeF₃2~5%.The present invention adds CeO in conventional enamel glaze₂And CeF₃The hardness of glaze and the adherence with steel plate can be improved, moreover it is possible to effectively prevent the generation of fishscale.

Description

Frit for porcelain enamel

Technical field

The present invention relates to a kind of glaze, and in particular to a kind of frit for porcelain enamel.

Background technology

Enamel coating method is that frit is coated in into surface of steel plate, by high-temperature roasting, enamel layer is sent out with steel matrix Raw reciprocation, forms coating process that is fine and close and being firmly combined with matrix.Frit for porcelain enamel is different from general ceramic glaze, and it is dashed forward The characteristics of going out is the frit for porcelain enamel not only surface smooth and beautiful appearance with glass performance, and with very excellent corrosion resistance, wear-resisting The property such as property, high temperature resistant, non-conductive property.It, which can be effectively improved, in metal base surface one layer of enamel layer of firing uses the longevity Life, and the contradiction of mechanical behavior under high temperature that stainless-steel sheet can not be provided simultaneously with and resistance to high temperature corrosion performance can be solved.Often The enamel coating of rule is all relatively thin, main to play a part of to protect parent metal.

Enamel coating steel plate there is also it is following two notable the problem of, first, steel plate when burning till, steel be in A condition, There is great solubility to hydrogen, a large amount of hydrogen produced in sintering process can be absorbed.But steel plate meeting in cooling procedure Occurs A-F phase transformation, the ability of parent metal dissolved hydrogen declines to a great extent, and the hydrogen separated out from steel is gathered in metal substrate with warding off The intersection of enamel coating, extension over time, the concentration more and more higher of hydrogen, when pressure exceedes the adhesion of enamel layer, enamel Layer will produce fishscale；Second, steel plate and enamel are two kinds of different compositions, different structure, the material of different properties, steel plate with Frit for porcelain enamel adherence is poor, easily occurs enamel layer and comes off.

The content of the invention

The technical problem to be solved in the present invention is to provide a kind of frit for porcelain enamel, the glaze hardness is high, close with stainless steel plate The property is good, moreover it is possible to effectively prevent the appearance of fishscale.

The technical scheme that the present invention is provided is to provide a kind of frit for porcelain enamel, by weight percentage, is made up of following components：

SiO₂50~65%, Al₂O₃20~30%, B₂O₃4~15%, Na₂O 1.2~1.5%, K₂O 1.3~ 1.6%th, CeO₂1~10%, CeF₃2~5%.

SiO₂It is base stock, the skeleton of enamel can be formed.Si-O keys bonding force is strong, and skeleton is complete, heat endurance, chemically-resistant Corrosive nature is good.

Al₂O₃So that frit for porcelain enamel viscosity under firing temperature increases, nucleus is formed smoothly, and crystal, which is grown up, to be obstructed, and forms big The microstructure of amount, improves the hardness of enamel layer.

B₂O₃With less surface tension and low modulus of elasticity, thus the mobility of melt is may advantageously facilitate, raising is warded off Glossiness, sophistication and the elasticity of porcelain.Also have fusing point low, play the effect of cosolvent.

K₂O、Na₂O is alkali metal oxide, is extremely strong cosolvent.

CeO₂In Ce4+ can replace SiO₂In Si4+, and Ce4+4f electronic shell energy is suitable with its 6S layers of electron energy, Electronics makes Ce-O keys have certain pliability easily in the two electronics Inter-layer motions.Therefore, when enamel layer is cooled down, steel When plate basic unit discharges hydrogen, Ce-O keys can extend, crystal space increase, can provide aggregation space to the hydrogen of release, Fishscale can effectively be prevented.

CeO₂Enamel layer viscosity can be improved when burning till, nucleus is smoothly formed, prevent crystal from growing up, form substantial amounts of crystallite Structure.CeF₃Addition enamel layer melt viscosity can be made to increase rapidly in cooling procedure is burnt till, greatly improve in enamel layer Micro crystal.Both add simultaneously, can substantially increase the hardness of enamel layer.

CeO₂And CeF₃Presence substantially increase dissolvings of the FeO in enamel layer, the catalyst as interfacial reaction makes boundary Face reaction is accelerated, promotion FeO and silicate reaction generation silicic acid iron compound in enamel layer, silicic acid iron compound formation anchor-shaped, So that enamel layer is tightly held on matrix, the adherence of enamel layer and matrix is added.

Preferably, the percentage by weight of each component is：SiO₂60%th, Al₂O₃25%th, B₂O₃7.2%th, Na₂O 1.3%th, K₂O 1.5%, CeO₂2%th, CeF₃3%.

Above-mentioned frit for porcelain enamel follows the steps below preparation：

1) SiO of formula ratio is weighed₂、Al₂O₃And B₂O₃It is pre-mixed ball milling, mixture homogeneity >=99.5%；

2) by other raw materials add step 1) mixed material in, mixing and ball milling, mixture homogeneity >=98%；

3) by step 2) mixed material feeding converter or tank furnace in found, temperature control is at 1250~1280 DEG C；

4) drilled a blasting hole after after material completely melting, the glass fiber that the liquid glass of melting is quickly pulled into 1.2~1.5m is carried out Detection, it is to found completion to have 2~3 sections in the 1m of glass fiber；

5) glass precursor solution melted is quickly poured into glass-hardened in water, produced after being filtered dry.

Compared with prior art, the present invention adds CeO in conventional enamel glaze₂And CeF₃The hardness of glaze can be improved And the adherence with steel plate, moreover it is possible to effectively prevent the generation of fishscale.

Embodiment

The present invention is further elaborated for specific examples below, but not as a limitation of the invention.

Following percentage is percetage by weight.

Embodiment 1

Formula：

SiO₂50%th, Al₂O₃20%th, B₂O₃15%th, Na₂O 1.2%, K₂O 1.3%, CeO₂10%th, CeF₃ 2.5%.

Preparation method：

1) SiO of formula ratio is weighed₂、Al₂O₃And B₂O₃It is pre-mixed ball milling, mixture homogeneity >=99.5%；

2) by other raw materials add step 1) mixed material in, mixing and ball milling, mixture homogeneity >=98%；

3) by step 2) mixed material feeding converter or tank furnace in found, temperature control is at 1250 DEG C；

4) drilled a blasting hole after after material completely melting, the glass fiber that the liquid glass of melting is quickly pulled into 1.2 is detected, It is to found completion to have 2 sections in the 1m of glass fiber；

5) glass precursor solution melted is quickly poured into glass-hardened in water, produced after being filtered dry.

Embodiment 2

Formula：

SiO₂65%th, Al₂O₃20%th, B₂O₃8.9%th, Na₂O 1.5%, K₂O 1.6%, CeO₂1%th, CeF₃2%.

Preparation method：

1) SiO of formula ratio is weighed₂、Al₂O₃And B₂O₃It is pre-mixed ball milling, mixture homogeneity >=99.5%；

2) by other raw materials add step 1) mixed material in, mixing and ball milling, mixture homogeneity >=98%；

3) by step 2) mixed material feeding converter or tank furnace in found, temperature control is at 1280 DEG C；

4) drilled a blasting hole after after material completely melting, the glass fiber that the liquid glass of melting is quickly pulled into 1.5m is detected, It is to found completion to have 3 sections in the 1m of glass fiber；

5) glass precursor solution melted is quickly poured into glass-hardened in water, produced after being filtered dry.

Embodiment 3

Formula：

SiO₂60%th, Al₂O₃25%th, B₂O₃7.2%th, Na₂O 1.3%, K₂O 1.5%, CeO₂2%th, CeF₃3%.

Preparation method：

1) SiO of formula ratio is weighed₂、Al₂O₃And B₂O₃It is pre-mixed ball milling, mixture homogeneity >=99.5%；

2) by other raw materials add step 1) mixed material in, mixing and ball milling, mixture homogeneity >=98%；

3) by step 2) mixed material feeding converter or tank furnace in found, temperature control is at 1260 DEG C；

4) drilled a blasting hole after after material completely melting, the glass fiber that the liquid glass of melting is quickly pulled into 1.3m is detected, It is to found completion to have 2 sections in the 1m of glass fiber；

5) glass precursor solution melted is quickly poured into glass-hardened in water, produced after being filtered dry.

Embodiment 4

Formula：

SiO₂55%th, Al₂O₃30%th, B₂O₃4%th, Na₂O 1.5%, K₂O 1.5%, CeO₂3%th, CeF₃5%.

Preparation method：

1) SiO of formula ratio is weighed₂、Al₂O₃And B₂O₃It is pre-mixed ball milling, mixture homogeneity >=99.5%；

2) by other raw materials add step 1) mixed material in, mixing and ball milling, mixture homogeneity >=98%；

3) by step 2) mixed material feeding converter or tank furnace in found, temperature control is at 1280 DEG C；

4) drilled a blasting hole after after material completely melting, the glass fiber that the liquid glass of melting is quickly pulled into 1.2m is detected, It is to found completion to have 3 sections in the 1m of glass fiber；

5) glass precursor solution melted is quickly poured into glass-hardened in water, produced after being filtered dry.

Reference examples 1

Formula：

SiO₂60%th, Al₂O₃25%th, B₂O₃7.2%th, Na₂O 1.3%, K₂O 1.5%, ZrO₂4%th, CoO 1%.

Preparation method：

1) SiO of formula ratio is weighed₂、Al₂O₃And B₂O₃It is pre-mixed ball milling, mixture homogeneity >=99.5%；

2) by other raw materials add step 1) mixed material in, mixing and ball milling, mixture homogeneity >=98%；

3) by step 2) mixed material feeding converter or tank furnace in found, temperature control is at 1260 DEG C；

4) drilled a blasting hole after after material completely melting, the glass fiber that the liquid glass of melting is quickly pulled into 1.3m is detected, It is to found completion to have 2 sections in the 1m of glass fiber；

5) glass precursor solution melted is quickly poured into glass-hardened in water, produced after being filtered dry.

Mild steel Q235A (C by above-described embodiment 1~4 and the frit for porcelain enamel of reference examples 1 using thickness as 2.3mm 0.2w%, S 0.05w%, P 0.04w%, Mn 0.8w%, Fe surplus) it is made enamelled pressed steel for matrix, carry out tack, resistance to Mill property and corrosion resistance detection.

1st, adhesive force is tested：

Marking 100 lattices of uniform size at intervals of 1mm with sharp blade on enamelled pressed steel surface, (cut is deep Degree control is ensureing the exposure of film lower substrate metal), the lattice number N1 that frit for porcelain enamel comes off, width is sticked in the frame region on film The adhesive tape for 24mm is spent, and ensures to be tightly combined between adhesive tape and the film of grid.After 5min, with a vertical face immediately Adhesive tape is opened, and the lattice number N2 that statistics film comes off again.Appraisal procedure is as follows：Using hundred-mark system, film adhesive force fraction =100- (N1+N2), adhesive force fraction is bigger, illustrates that adhesive force is better.

2nd, wearability test：

Enamelled pressed steel is put into oscillating mill after continuous shaking grinding 2h and taken out, the corner angle and table of enamelled pressed steel are observed Whether the film layer in face, which has, comes off.

3rd, corrosion resistance is tested：

Enamelled pressed steel is placed in salt air corrosion case, with after 5% sodium-chloride water solution splash 2h at 35 DEG C, taken out again Be placed in the climatic chamber that another temperature is 40 degree, relative humidity is 80%, observe its how long after surface There is exception, the time is longer, illustrates that the corrosion resistance of film layer is better.

Result of the test see the table below 1

As can be seen here, the enamelled pressed steel that frit for porcelain enamel of the present invention is made has excellent adherence, wearability and corrosion-resistant Property.

Claims (3)

1. frit for porcelain enamel, it is characterised in that：By weight percentage, it is made up of following components：SiO₂50~65%, Al₂O₃ 20 ~30%, B₂O₃4~15%, Na₂O 1.2~1.5%, K₂O 1.3~1.6%, CeO₂1~10%, CeF₃2~5%.

2. frit for porcelain enamel according to claim 1, it is characterised in that：The percentage by weight of each component is：SiO₂60%th, Al₂O₃25%th, B₂O₃7.2%th, Na₂O 1.3%, K₂O 1.5%, CeO₂2%th, CeF₃3%.

3. frit for porcelain enamel according to claim 1 or 2, it is characterised in that：Follow the steps below preparation：

1) SiO of formula ratio is weighed₂、Al₂O₃And B₂O₃It is pre-mixed ball milling, mixture homogeneity >=99.5%；

2) by other raw materials add step 1) mixed material in, mixing and ball milling, mixture homogeneity >=98%；

3) by step 2) mixed material feeding converter or tank furnace in found, temperature control is at 1250~1280 DEG C；

4) drilled a blasting hole after after material completely melting, the glass fiber that the liquid glass of melting is quickly pulled into 1.2~1.5m is detected, It is to found completion to have 2~3 sections in the 1m of glass fiber；

5) glass precursor solution melted is quickly poured into glass-hardened in water, produced after being filtered dry.