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Glass ﴾enamel﴿ Material and Enameling

Technology
Minos Chen
Global Site Service & Export Manager @ ALLSOURCE + Follow
Published Aug 17, 2019

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（glass lined cover for H2SO4 waste acid concertration）

1. Definition of glass-lined steel

Glass-lined steel is not a simple product. It is a sophisticated composite. The glass-lining is

coated on a metal surface by a special process. The coating is a non-metallic inorganic
material (glassed-steel-enamel), which undergoes a physical & chemical reaction at high
temperature and is firmly combined to steel substrate by chemical bonding.

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 （covalent bond sttructure of glass lining）

The advantages of the original two materials (metal and glass) are fully exerted, and the
shortages of materials are compensated by each other, thus becoming a new kind of composite
material with comprehensive properties against pressure, impact, corrosion and temperature
difference. And this glass is smooth and easy to clean, chemical inert, and isolated to
electricity.

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(glass lined cover)

There are four main characteristics of the definition: 1) indicating the composition, consists of
metal and glass (enamel); 2) physical and chemical reaction at high temperature; 3) make the
two materials adhere to each other firmly by chemical bonding; 4) composite material with
comprehensive performance against impact, chemical corrosion, pressure, temperature etc.

2. The Main Difference Between Glass-lined-steel and Porcelain-enamel

 (daily use enamelled products)

2.1. Material difference

Porcelain enamel generally uses a steel sheet of 1 mm or less while Glass-lined steel uses a
thick medium plate of 6 mm or more.

(carbon steel plate in glass lined steel factory)

Porcelain enamel uses enamel-glaze while glass-lined steel uses glassed-steel-enamel.

Comparison table of components of glassed-steel-enamel and enamel glaze (unit%)

(glass materials)

It can be seen from the above table that the SiO2 content of the glassed-steel-enamel is higher
than that of the enamel-glaze, and the content of the alkali (R2O RO) is lower than that of the
enamel-glaze. Therefore, the glass lining formed by firing the glassed-steel-enamel has a more
stable and firmer Silicon tetrahedron, and thus has a higher firing temperature and better
corrosion resistance.

(steel substrate prepared for glass lining process)

2.2. Production process difference

Most of the enamel products are formed by pressing and without welding, while the glass-
lined products are formed by pressing, cold working and welding; the surface pretreatment of
enamel products is generally washed with acid, and the glass-lined products are generally
cleaned with shot-blast; The enamel products has a lower enameling temperature than the
glass-lined products, thinner porcelain layer, and shorter firing time.

2.3. Different Applications

The corrosion resistance of enamel products is weaker than that of glass-lined products.
Therefore, it is generally used for daily use and civil use, while the glass lined products are
industrially used and have strong corrosion resistance.

In enameling terminology, glass-lined-steel enamel (glass) is defined as: enamel with

performances of strong anti-corrosion, temperature & pressure resistance.

(glass lined reactor under critical gaseous corrosion for PAC

production)

3. Glassed-steel-enamel Chemical Composition & Mineral Raw Materials

The raw materials of the glassed-steel-enamel are summarized as seven types or seven doses.
A simple list of the various raw materials for each component is as follows:

The main components of the composition of the glassed-steel-enamel

Different matrix agents form enamels with different properties. Silicate enamel with SiO2 as
matrix agent has good acid resistance; phosphate enamel with P2O5 as matrix agent can resist
hydrofluoric acid (HF); borate enamel with B2O3 as matrix agent has porcelain gloss and
compact performance; Zirconium enamel with ZrO2 as matrix agent has good alkali
resistance. Usually, SiO2 and B2O3 are collectively used as a base agent for enamel, which is
named borosilicate enamel that is widely used for most of glass-lined reactors. Because it has
good chemical stability and mechanical strength, and the production process is easy to control
and the cost is relatively low. The increase of ZrO2 and TiO2 content in the formulation
enhances and improves the corrosion resistance of the enamel to meet the requirements of
much better performance. Reducing the amount of alkali in the formulation is also very
effective in improving the corrosion resistance of the enamel, but the expansion coefficient is
reduced. If without good heat preservation cooling process, it is easy to cause glass cracking.
Therefore, the high-quality acid-resistant enamel needs to be insulated and cooled slowly
after firing. Because, at this time, the enamel changes from a plastic state to a brittle state, and
once the stress caused is greater than the tensile strength of the enamel, it will cause glass
cracking.

To use good physicochemical properties enamel, it is necessary to have a good processing

system to ensure that high-quality glass lined products can be made.

4. The Difference Between Enamel-material and Glass-lining

(difference of glass material and glass lining)

Enamel is similar to glass, and the glass lining is something that the enamel frit plus the
grinding material, after grinding, coating and firing, a large amount of crystals are formed in
the enamel-glass-body, which changes the structure of the enamel.

The structure of the glass lining is mainly a regular mixed polyhedron formed by a plurality of
networks, such as a continuous grid of [SiO4], [BO3], [BO4], etc., and the cations in each
agent of the enamel components enter the gap of the outer body of the glass lining network in a
coordination relationship, so the order of the glass lining is better than that of the enamel
material (frits).

Layered schematic diagram about lining of glass lined steel

 (strutural layers of glass lined steel)

The glass lining is a general term for the entire glass lined enamel layer. It consists of five
layers: 1) the diffusion interpenetrating layer of metal and ground coat, that is, the complex
layer of adhesion; 2) the ground coat layer: 3) the diffusion interpenetrating layer between
ground coat & cover coat, which is a chelate interpenetrating layer; 4) the cover coat layer; 5)
the outer surface of glass lining.

The firing temperature and firing time determine the thickness of the complex adhesion layer
and the chelate interpenetrating layer, and the mechanical strength of the glass lining depends
on the quality these two layers (complex adhesion layer and the chelate interpenetrating
layer). So firing temperature & firing time are key factors of enameling quality.

5. The Application of Glaze Slip

(wet praying in enamelling proccess)

The glaze slip released by wet grinding ground-coat-frit is usually stored for a period of time
(aging) to ensure a certain pH, consistency, and reasonable electrolyte content which is
suitable for enameling.

As the glaze slip aging, in addition to the electrolyte, the clay particles will continue to
colloidally disperse, thereby increasing the puffing and plasticity and improving the coating
performance. This process can also release the air dissolved in the glaze slip during grinding,
and lead to a favorable effect on glass lining.

With dry frit powder, soaking for a day, then fully stir and sieve to use. Some manufacturers
only soak the power for less than an hour, and stirring sloppy (not stir evenly), then use
without sieve, which seriously affecting the application performance of the spraying, resulting
in defects such as color difference, unevenness surface, etc.

It is necessary to control the volume weight of the glaze slip when spraying. The ground coat
slip is generally 165-170g/100ml, and the cover coat slip 164~168g/100ml. In the case when
spray smoothly, the higher the volume weight of the glaze slip, the better, because the glaze
slip with higher volume weight is with less moisture, which is beneficial to the quality of
spraying & drying.

Generally, most manufacturers pay great attention to the management of glaze slip and unify the
distribution, which guarantees the quality of glaze slip. Whereas, some manufacturers allow
their sprayers to adjust the glaze slip with water by their own freely, ignoring the control of
the olume weight, seriously affecting the quality of the glass lining after firing.

The glaze slip is stored in a container, and as time passes, splitting and delamination occurs.
Refer to following diagram:

(static layering of glass slip)

This schematic diagram clearly shows that the upper and lower layers of the glaze slip have
different compositions and different volume weight. pH value, α (linear expansion
coefficient), dispersed phase, the retention increases from bottom to top; the softening point η
(viscosity) decreases from bottom to top.

If apply the glaze slip not uniformly stirred for powder sprayin, it is obvious that the glaze has
changed its original performance, and many defects accompany it, which seriously affects the
quality of the glass lining.

When spraying large-scale products, a huge amount of glaze slip is required. If there is no
agitation in the spray glaze slip tank, which tends to cause precipitation and different
components, and the glass lining will have defects after firing. It is recommended that a
compressed air plastic tube be dipped into the glaze slip container for continuous gas agitation
to ensure the quality of the spraying.

(pressurized kettle for wet glass spraying)

The glaze slip should be used shorterly after grinding, without adding clay, yet adding an
appropriate amount of electrolyte, such as BaC12、Cacl2、Na2NO2, etc. Thus adjust the
consistency of the glaze slip, and improve to set up suspension system, then the glaze slip is
sprayed from a pressurized tank. This is one of the best ways to make sure a high quality glass
lining. It can improve the color and luster of the glass surface, also, enhance the acid and
alkali resistance.

6. Firing of Glass Lined Steel

The firing process of glass-lined steel is a key manufacturing process for the quality of glass-
lined products.

(glass lined pipes standing for drying before firing)

The production process of glass-lined products is very complicated. And quality control
consists of control of quality of the steel plate, raw manufacturing processes (cutting, bending,
welding etc.) and surface treatment (e.g. shot-blast) of steel substrate, the quality of the
enamel, the coating operation, the firing process, the performance of the firing furnace etc.
Among these factors, firing technology is the key concern.

The physical and chemical combination between metal and enamel is achieved through the
enameling process.

With a low firing temperature, the viscosity of the enamel melt increases, the gas is not easily
to be released from the glass lining, the pores and bubbles in the layer and the surface are
excessive. On the contrary, when the firing temperature is too high, and it’s too short time for
each firing stage to be performed. Without proper and sufficient physical and chemical
interaction, resulting in defects such as poor adhesion, difficulty in formation of
interpenetrating layers, color irregularity, scorching, over-burning etc.

(firing defect_color difference)

One of the core technologies for international manufacturers of glass-lined products:

"controlled firing technology" with the application of computer technology. Computer is
programed to control the whole processes of heating, heat preservation and cooling according
to a reasonable firing curve of different enamel formula.

The firing and cooling diagrams have three heat preservation stages (400℃~450 ℃,
600℃~650 ℃, peak firing temperature). The purpose of heat preservation stages I and II is to
ensure sufficient time for the gas to emit from the glass lining, leaving less defects, no
porosity, bubbles, etc., and continuously forming a dense layer (ground coat and metal) and
interpenetration layer (cover coat and ground coat); the III stage is the final firing temperature,
which is used to accelerate the physicochemical reaction, so that the gas can emit, and the
pores are completely eliminated, and the glass surface is smooth. At the same time, it helps to
creates advantage for interactions within the polyhedral structure (consisting of silicon
oxide tetrahedron [SiO4], boron oxygen triangle [BO3], boron oxide tetrahedron,
aluminoxyoctahedron [AlO8]), resulting in good quality of complex adhesion layer,
chelate interpenetrating layer as well as overall quality of glass lining.

（firing curve）

According to a proper firing curve, the glass lining can avoid many defects, improve the gloss
and smoothness of its surface, and can improve the physical and chemical properties, and
especially corrosion resistance. If the entire glass lining is ground, it can be found that there
are few or even no pores visible to the naked eye. At the end of the firing, the three phases of
metal, ground coat and cover coat, are firmly combined as one thing, through a thorough
physical and chemical reaction, and become an excellent composite product.

Let’s emphasize here that the firing of ground coat is a key process to combine two different
materials, non-metal and metal, into one thing.

With ground coat burned, creating positive conditions for cover coat firing, greatly reduces
possible defects, greatly improves the survival rate of the final product, and the quality is
effectively assured.

For furnace with controllable temperature, the heat preservation stages “I” and “III” are more
important and more necessary than stage “II”(refer to above firing curve)

Some regional manufacturers do not have temperature-controllable-furnace. Therefore, their

product quality differs a lot from international well-known manufacturers

Some manufacturers define this “right time” for removing glass lined products from furnace –
when brightness of the surface of glass lining is as red as that of the furnace wall, and it is
done. But this is not correct: 1) insufficient firing. When the surface of the glass lining
achieves the peak firing temperature, but due to glass is a poor heat conductor, the temperature
of the inner layers have not reached the required firing temperature, thus the physicochemical
reaction is not completed; 2) There is no holding time if removing products from furnace one
achieving firing temperature. In this case, the air (from steel and glass material) will not be
released completely, the pores of glass lining will not eliminated, so that the glass cannot be
smooth or flat enough. Also, the chemical bonding is not strong enough, and the complex
adhesion layer and the chelate interpenetrating layer are poorly formed. The polyhedral
network structure is weak too. Therefore, it is beneficial and necessary to appropriately
extend a holding time at peak firing temperature for the concern of a quality final product.

When the product reaches the firing temperature but cannot be fired (the electric furnace does
not have a temperature limit facility). If the temperature is increased, the firing time is
prolonged, which may cause over-burning, it will cause many defects to the porcelain layer. If
the bottom glaze is burnt, the face glaze will boil again to result in pores, bubbles and the
enamel layer will not close, which will cause the stress increase in the porcelain layer, the
elasticity to decrease, the porcelain surface gloss to decrease, and the adhesion to decrease.
Therefore, high temperature is often more harmful.

In summary, different enamels have different firing ranges and different reasonable firing
curves. Following to the designed reasonable firing curve, the gas generation, escape and
close are more thoroughly, the physicochemical reaction is more complete, the formation of
the complex layer and the interpenetrating layer will be better, and the stress in the porcelain
layer is reduced , improve the elasticity of the porcelain layer which will prevent the
generation of defects, boost the physical and chemical properties of the porcelain layer, and
even ensures the quality and stability of the glass lined products.

7. Post-firing Cooling of Glass Lined Products

(removing vertical fired glass lined vessel and cover after cooling in
furnace)

After firing, the product needs to be cooled slowly under heat preservation. Due to the
different expansion coefficients of the two different materials (metal and glass lining) during
cooling, the expansion stress is created. The faster the cooling rate, the higher the expansion
stress can be. Therefore, cooling gradually and slowly is required to avoid permanent stress.

The glass lining does not generate stress in the molten state. As the temperature decreases, the
glass begins to cure and generate stress, and in a tensile stress state: ①580～500℃, which
requires heat preservation, i.e. cooling at a slower or slower speed; when the temperature
drops to ②400℃, with certain holding time for heat preservation, glass failure at welded
joint can be avoid. This is beneficial and effective to improve quality of glass lined products,
especially for large-scale ones. This is equivalent to a dehydrogenation treatment for the glass
lined products, eliminating the hidden dangers in later application of the products

The enamel with high acid resistance performance has higher percentage of SiO2, higher
viscosity and higher resistance to release air, thus decreases the speed of physicochemical
reaction. Therefore, it is beneficial to extend the heat preservation time at final firing stage.
And, insulated cooling is more important, because glass has a smaller expansion coefficient
than steel. The faster the cooling rate, the higher expansion stress will be. That is why cooling
in free air often causes glass failure.
(less favored production technology: horizontally firing & cooling in
free air)

To make high-quality glass-lined products, you must have: 1) good tooling equipment; 2) good
raw materials; 3) good processing technology; 4) good working condition; and, 5) well-
trained workers. It is what we called the five key factors affecting product quality, among
which people are the most essential and most important factor.

Minos Chen

Project Manager

MOBILE :+86-13815980995

Email: minos.chen@creas.cn

Website: www.creas.cn/en/

Suzhou CREAS Fluid Equipment Co., Ltd.

Jingjiang Allsource Imp. & Exp. Co.,Ltd.

10 · 4 Comments

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mohsen mohammadipour 5mo

how can i solve this problem?
tnx.
Like Reply 1 Like

mohsen mohammadipour 5mo

hi.
thanks for your information.
i have a QUESTION:
why does ground layer jumps after applying top coat ?

Like Reply 1 Like

mohsen mohammadipour 4mo

Minos Chen
hi
that was a perfect guidness. i will do it and see the result.
thanks a lot.
Like Reply
 Minos Chen 4mo
Reason: problem of temperature control, firing temperature of upper coats are higher than
necessary, which some may call it "over‐firing". This is very detailed technical points. And may
worth a lot of money : ﴿ Normally, there are about 1~2 ground coats, 4 or more cover coat unit
it pass thickness and spark test. The lower coat will endure higher temperature. To avoid it, as for
firing temperrature, ground coat will be about 100C higher than cover coat, and each cover coat
will be about 10C lower than previous cover coat. That is, ground coat about 920C, 1st cover
coat 830C, 2nd cover coat 820C, 3rd cover coat 810C, and the rest cover coat if any are all
810C.
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