Glasses

(C) Dept of Applied Chemistry - SVCE 1

Định nghĩa thủy tinh

“Thủy tinh là sản phẩm vô cơ nóng chảy được làm

quá lạnh đến trạng thái rắn không kết tinh”
- Những chất lỏng khi làm quá lạnh có khả năng tạo
thủy tinh phải có độ nhớt tăng nhanh và liên tục
theo chiều giảm nhiệt độ từ vài trăm poise đến 1014
poise.
• Độ nhớt của các chất theo nhiệt độ
 Phân loại thủy tinh vô cơ theo thành phần
và đặc tính
1 Thủy tinh đơn nguyên tử
• Chứa một loại nguyên tố hóa học. Đó là các nguyên tố như
S, Se, As và P
• Ví dụ: Để có được thủy tinh từ lưu huỳnh ta làm lạnh nhanh
lưu huỳnh nóng chảy:
- Làm lạnh đến nhiệt độ phòng sẽ được sản phẩm giống cao su
nhưng trong suốt và không tan trong H2S;
- Làm lạnh đến -11o C nó sẽ đông cứng có chiết suất 1,998.
2 Thủy tinh oxit
• Thủy tinh đi từ oxit như: B2O3, SiO2, GeO2, P2O5
• Các oxit không có khả năng tạo thủy tinh nhưng khi liên hợp
với những oxit tạo thủy tinh thì khả năng tạo thủy tinh của nó
tăng lên như: Al2O3, Ga2O3, Bi2O3, TiO2, MoO3 , WO3
• Trong thực tế có nhiều thủy tinh chứa đồng thời 2 hoặc 3 oxit
tạo thủy tinh.
3 Thủy tinh halogen
• Hai halogen có khả năng tạo thủy tinh là F2 và Cl2.
• Các Fluorit khác có thể đưa vào thủy tinh như AlF3, SrF2,
BaF2, MgF2, BeF2. Các Fluorit kim loại kiềm làm giảm đáng
kể độ bền hóa của thủy tinh.
• Từ Cl chỉ có ZnCl2 là có thể tạo trạng thái thủy tinh một,
nhưng hệ số giãn nở nhiệt của nó rất cao (323.10-7)
4 Thủy tinh khancon
• Là các loại thủy tinh đi từ các hợp chất của lưu huỳnh, selen
và telur (GeS2, As2S3, As2Se3, GeSe2, P2Se3).
• Thủy tinh khancon không trong suốt, dễ nóng chảy và
nhanh chóng kết tinh, do đó muốn đạt trạng thái thủy
tinh phải làm lạnh thật nhanh, khoảng 200oC/s.
• Thủy tinh khancon thể hiện độ dẫn điện như chất bán dẫn
nên được dùng trong lĩnh vực bán dẫn.
• Thủy tinh khancon có nhiệt độ nóng chảy cao ~ 1700o C từ
các hệ: Ni – Ge – Se ; Mn – Ge – Se ; Ni – Zn – Se; Ni –
Ge – S ; Zn – Ge – Se .
5 Thủy tinh hỗn hợp
• Thủy tinh đi từ hỗn hợp các chất có khả năng tạo thủy tinh:
- oxit – halogen : PbO- ZnF2 –TeO2 ; ZnCl2 - TeO2
- oxit – khancon : Sb2O3 – As2S3; As2S3 – As2O3 – MemOn (
MemOn: Sb2O3, PbO, CuO).
- Halogen – Khancon:As – S – Cl; As – S – Br; As– S – I ;
As – Te – I; As - S -Cl –Br –I
Introduction

“Glass is an amorphous, hard, brittle, transparent or translucent, super-cooled

liquid, obtained by fusing a mixture of a number of metallic silicates, most
commonly Na, K,Ca and Pb”. It possesses no sharp melting point, crystalling
structure and definite formula

Represented as xR2O . yMO . 6SiO2

R = monovalent alkali metals like Na,K

M = Divalent metals like Ca, Pb,Zn, etc
x & y = whole numbers

• Approximate composition of ordinary glass(Soda lime glass) is

Na2O . CaO . 6SiO2
• In some glasses, SiO2 may be replaced by Al2O3 . B2O3 . P2O5 , etc

(C) Dept of Applied Chemistry - SVCE 9

General Properties of glass
✓ Amorphous Solid (chất rắn vô định hình)
✓ No definite melting point
✓ Very brittle (giòn)
✓ Softens on heating
✓ Can absorb, reflect and transmit light
✓ Good electrical insulator
✓ Affected by alkalis
✓ Not affected by air,water,acid or chemical reagents . But soluble in HF which
converts into SiF4
✓ Possesses high compressive strength and since it doesn’t have any crystalline
structure , no slippage between planes can occur
✓ Light in weight because it has homogeneous internal structure similar to liquids
(C) Dept of Applied Chemistry - SVCE 10
Phân loại thủy tinh silicate

1. Soda-lime or soda glass

2. Potash lime or hard glass
3. Lead glass or Flint glass
4. Borosilicate glass or Pyrex glass or Jena glass
5. Alumina silicate glass
6. Optical or Crookes glass
7. Glass wool
8. Quartz glass
9. Opal glass

(C) Dept of Applied Chemistry - SVCE 11

Phân loại thủy tinh silicate: Soda-lime (or) Soft glass

Raw Materials
• Silica
• CaCO3
• Soda ash
Properties
• Low cost
• Resistant to water
• Attacked by acids
Composition
• Melts easily
Na2O . CaO . 6SiO2
• Moulded easily to any shape
• Poor thermal & chemical resistance

Uses
Window glasses, electric bulbs, bottles, jars, table wares etc.,

(C) Dept of Applied Chemistry - SVCE 12

Phân loại thủy tinh silicate: Potash-lime (or) Hard glass

Raw Materials
• Silica
• CaCO3
• K2CO3
Properties
• High Melting point
• Not attacked by acids, alkali and other solvents Composition
• Costlier than soda-lime glass K2O . CaO . 6SiO2

Uses
Combustion tubes (ống chịu nhiệt), chemical apparatus (dụng
cụ thí nghiệm)

(C) Dept of Applied Chemistry - SVCE 13

Phân loại thủy tinh silicate:Lead glass (or) Flint glass
Raw Materials
• Silica
• Lead Oxide
• Potassium Oxide
Properties
• Bright, lustrous (sáng, bóng láng) and possesses high
specific gravity
• Expensive to manufacture , than ordinary lime-soda glass
Composition • Lower softening temperature than soda-lime glass
K2O . PbO . 6SiO2 • Higher refractive index (chỉ số khúc xạ cao) and excellent
electrical properties

Uses
• High quality table wares, neon sign tubings , optical lenses
• High dense glasses are used for windows to protect from
X-rays and gamma rays

(C) Dept of Applied Chemistry - SVCE 14

 Phân loại thủy tinh silicate: Pyrex-glass (or) Jena glass

Raw Materials K2 O 3 %
Al2O3 3 %
• Silica B2O3 13 %
Na2O 0.5 %
• Small amount of alumina
• Some oxides
Properties SiO2 80.5 %
• Substitution of alkali (Na2O) and basic alkaline
earth oxides(CaO) of the soda glasses by boron
and aluminium oxides results in low thermal co-efficient
• High softening point and excellent resistivity(shock proof) Composition
• High chemical resistance

Uses
Industrial pipeline for corrosive liquids, gauge glasses (thuỷ
tinh điện trở suất cao), superior laboratory apparatus etc.,

(C) Dept of Applied Chemistry - SVCE 15

 Alumino Silicate glass

Raw Materials CaO 5 %

MgO 9 %
• 5 % more of alumina B2O3 7 %
Na2O + K2O 1 %
• Addition of alumina makes glass heat resistant
Properties
• Exceptionally high softening temperature Al2O3 23 %
SiO2 55 %
• Chemically durable
• Resistance to hydrolysis
• Affected by moisture due to high surface area
Composition
Uses
• High pressure mercury discharge tubes, chemical
combustion tubes, specific domestic equipments
• Fibre glass

(C) Dept of Applied Chemistry - SVCE 16

Phân loại thủy tinh silicate: Optical, Quartz and Opal Glass
Optical glass Quartz glass Opal glass (kính
(quang học) (thạch anh) trắng đục)

Raw Material Raw Material Raw Material

• Phosphorous and lead
silicate together with small
amount of cerium oxide
Properties
• Low melting point
• Soft
• Chemical-resistance
• Durability lesser than
ordinary glasses
• Absorbs UV light
• Crystalline silica fused at • NaF (or) CaF2 (or)
1900oC Ca3(PO4)2 (or) SnO2
Properties Properties
• Outstanding resistance to • Translucent white or milky
thermal shock and glasses (trắng mờ)
chemicals • Transparent when in liquid
Uses • Opaque when cooled
• Special lab-ware
• Crucibles (tôi luyện)
• Reaction tubes

Uses
Optical lenses

(C) Dept of Applied Chemistry - SVCE 17

Phân loại thủy tinh silicate: Glass wool

• Fibrous wool-like material, composed of

intermingled fine threads (or) filaments of glass
• Alkali free
• Glass filaments are obtained by forcing molten
glass through small orifices which measures about
0.0005 to 0.0007 mm in diameter
Properties
• Very good fire-proof and heat proof (chịu nhiệt và chịu lửa)
• Very low electircal conductivity and thermal conductivity (dẫn điện và nhiệt thấp)
• Resistance to water and most chemicals
• Tensile strength is 8X of steel (bền kéo)
Uses
• Heat insulation purpose (cách nhiệt)
• Electrical and sound insulation (cách điện và âm thanh)
• Filtration of corrosive liquids like acids (lọc chất lỏng ăn mòn)
• Manufacturing fibre-glass, by blending with plastic resins (tạo sợi thuỷ tinh khi
hết hợp với plastic)
(C) Dept of Applied Chemistry - SVCE 18
Quy trình công nghệ sản xuất thủy tinh
Nguyên liệu

Phối liệu Thủy tinh tái chế

Nấu thủy tinh

Tạo hình sản phẩm

Ủ thủy tinh

Sản phẩm không đạt

Kiểm tra chất
lượng

Sản phẩm 19
 Nguyên vật liệu và phối liệu

• Nguyên liệu dùng sản xuất thủy tinh chia làm 2 nhóm: Nhóm
nguyên liệu chính và nhóm nguyên liệu phụ.
• Nguyên liệu chính có khả năng cung cấp cho thủy tinh các oxit
kiềm, kiềm thổ, oxit axit.
• Nguyên liệu phụ: chất nhuộm màu, chất gây đục, chất khử bọt …
• Thực tế để nấu thủy tinh người ta thường sử dụng các loại
nguyên liệu: Cát, đá vôi, trường thạch, đôlômit, sôđa,
borat…và trong nhiều trường hợp có cả các oxit tinh khiết.
SiO2: thành phần chủ yếu của đa số các thủy tinh công nghiệp
thông thường (50-80% SiO2). Nó cung cấp cho thủy tinh độ
bền cơ, bền nhiệt, bền hóa.’
B2O3
• Làm tăng độ bền cơ, bền nhiệt, bền hóa của thủy tinh
Al2O3
• Giảm tốc độ và khả năng kết tinh của thủy tinh
• Có ảnh hưởng thuận lợi đến biến thiên độ nhớt theo nhiệt độ
• Tăng độ bền cơ bền hóa.

(C) Dept of Applied Chemistry - SVCE 21

Na2O
• Giảm tính chất cơ học, hóa học, bền hóa,..
• Hạ thấp nhiệt độ nấu, tăng tốc độ hòa tan các hạt cát, tăng
tốc độ khử bọt do hạ thấp độ nhớt của thủy tinh.
K2O
• K2O làm giảm khả năng kết tinh của thủy tinh , làm cho
thủy tinh ánh hơn và sắc thái đẹp hơn.
Li2O
• Li2O làm tăng độ bền hóa, giảm hệ số giãn nở nhiệt của
thủy tinh. Li2O làm giảm độ nhớt của thủy tinh nhiều hơn
các ôxyt kim loại kiềm khác.
CaO
• Giúp cho quá trình nấu và khử bọt thêm dễ, làm cho thủy
tinh chịu được ăn mòn hóa học
(C) Dept of Applied Chemistry - SVCE 22
BaO
• BaO làm thủy tinh ánh đẹp, tăng trọng lượng riêng, tăng
chiết suất
PbO
• Thủy tinh chì dễ nấu, dễ khử bọt. Các sản phẩm thủy
tinh chứa chì có trọng lượng riêng lớn, chiết suất cao,
ánh đẹp, dễ mài và đánh nhẵn nhưng kém bền hóa và
gây độc cho người nấu.
ZnO
• ZnO làm giảm hệ số giãn nở nhiệt, tăng độ bền hoá,
bền nhiệt của thủy tinh

(C) Dept of Applied Chemistry - SVCE 23

 Raw materials of glass
Sl.N Name of the Source of the element Name of the
Glass Components o element glass produced
Sodium
(Na), 14
1 Sodium (Na) Na2CO3,Na2SO4 Soft glass
Others, 2.7 Potassium
(K), 0.3 2 Potassium (K) Potash, K2CO3,KNO3 Hard glass
Calcium (Ca),
9 3 Calcium (Ca) Lime, limestone Glass with
high RI

Silica, 70 4 Barium (Ba) BaCO3 Glass with

Barium (Ba),
4 high RI
5 Lead Litharge, red lead Flint glass
6 Zinc Zinc Oxide Heat & Shock
proof glass
dium (Na) Potassium (K) Calcium (Ca)

rium (Ba) Silica Others 7 Borate Borax, boric acid Heat & shock
proof glass

8 Silica Sand, quartz

Colors Ferric Salt
Yellow
Green Ferrous and chromium
Blue Cobalt salt
98.33X + 0.7Y + 66.25.Z + 0.46T = 69.23 25
Glass Manufacturing

Manufacturing of glass consists of following high level steps

1. Melting (nấu chảy)

a. Pot furnace (lò nồi)

b. Tank furnace (lò bể)

2. Forming and shaping (tạo hình)

3. Annealing (ủ)

4. Finishing (hoàn tất)

(C) Dept of Applied Chemistry - SVCE 26

Melting

• Raw materials in proper proportions (sand, soda ash

and lime stone ) are mixed and finely powdered
• The homogenous mixture known as Batch is fused with
some broken glass , called “Cullet” in any of the two
types of furnaces
• The homogeneous mixture is melted either in
a. Pot furnace or
b. Tank furnace
• The batch melts and fuses at 1600 -1800oC

(C) Dept of Applied Chemistry - SVCE 27

Melting: Pot furnace

✓ Two types of pots are used

Figure showing Pot furnace
a. Open crucible type pot
b. Closed covered type pot
✓ Generally closed covered type pot is used
C D A B
✓ Pot is placed in a circle around a central
Hot Air opening in its bottom
✓ Heated by burning producer gas and air
✓ Roof of the pot is constructed with refractory
Hot Gases
material which also reflects the heat
✓ Also called as batch process

(C) Dept of Applied Chemistry - SVCE 28

 Melting: Tank Furnace
Fuel gas and air being
✓ The “batch” is melted in the tank using heated by hot checker
Burning fuel gas
work

producer gas and air Molten gas

✓ It follows “regenerative system of heat

A B C D
economy”
✓ Air and fuel is passes through A & B
Air Fuel gas Fuel gases
✓ The burnt gases are deflected by the roof
Figure showing tank furnace
and “batch” gets melted
✓ Hot waste gas escapes through firebricks
C&D
✓ The direction of the fuel gas & air is reversed through C & D , which absorbs the
heat of the waste gas and burns
✓ The waste gas now escapes through A & B
(C) Dept of Applied Chemistry - SVCE 29
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Forming & Shaping, Annealing and Finishing

✓ Molten gas is converted to desired shape by blowing or moulding or pressing

between rollers - “Forming and Shaping”
✓ Articles are then cooled gradually at room temperature. - “Annealing”
The longer the annealing period better the quality of glass
✓ After annealing, the articles are subjected to cleaning, polishing, cutting, sand
blasting etc., - “Finishing”

(C) Dept of Applied Chemistry - SVCE 35

 Glassmaking

1. The ingredients for glass are mixed, and along with a proportion of
cullet (broken glass), are added to a bath furnace, where they are
heated to about 1500°C and fused together.
2. Molten glass is fed as ‘gobs’ to an automatic bottle or jar making
machine.
3. A hot gob is first made into a parison or blank shape (by either pressing
or blowing), which is then blown to the final bottle or jar shape. Surface
coatings (sc) may be applied while hot.
36
4. The bottles or jars pass into a lehr (an annealing oven), where they
are first reheated to soften the glass to remove stresses, and then
cooled gradually to prevent stresses developing.
5. The bottles or jars are inspected and tested to meet quality
standards. Bottles not passing the quality checks are broken and
returned to the furnace as cullet. Cullet reduces the amount of
energy required to melt the glass ingredients.
6. Bottles passing inspection and testing are packed for dispatch to
where they will be filled, capped, and labeled.

37
Shaping Processes in Glassmaking
➢ Shaping processes to fabricate these products can be
grouped into three categories:

1. Discrete processes for piece ware (bottles, jars,

plates, light bulbs) (quá trình gián đoạn)

2. Continuous processes for making flat glass (sheet

and plate glass) and tubing (laboratory ware,
fluorescent lights) (quá trình liên tục)

3. Fiber-making processes to produce fibers (for

insulation and fiber optics) (quá trình tạo sợi)

38
 Shaping of Piece Ware
➢ Ancient methods of hand-working glass included glass blowing.
➢ Handicraft methods (pp thủ công) are still used today for making
glassware items of high value in small quantities. However, most
modern glass shaping processes are highly mechanized technologies
for producing discrete pieces in high quantities.
➢ Piece Ware Shaping Processes
1. Spinning (quay) – similar to centrifugal casting of metals
2. Pressing (nén) – for mass production of flat products such as
dishes, bake ware, and TV tube faceplates
3. Press-and-blow (nén – thổi) – for production of wide-mouth
containers such as jars
4. Blow-and-blow (thổi)- for production of smaller-mouth containers
such as beverage bottles and incandescent light bulbs
5. Casting (đúc) – for large items such as large astronomical lenses
that must cool very slowly to avoid cracking. 39
Spinning of funnel-shaped glass parts such as back sections of cathode
ray tubes for TVs and computer monitors:
(1) gob of glass dropped into mold; and
(2) rotation of mold to cause spreading of molten glass on mold surface
40
Pressing of flat glass pieces:
(1) glass gob is fed into mold from furnace;
(2) pressing into shape by plunger; and
(3) plunger is retracted and finished product is removed (symbols v
and F indicate motion (velocity) and applied force)

41
1. A gob of hot glass drops into the blank (parison) mould.
2. The mould is sealed shut by a ‘base’ part and a plunger pushes the glass
into the mould (made from iron).
3. The glass is shaped into a ‘blank’ and also pushed into the neck finish by
the plunger. This part of a jar or bottle is finished to its final shape at this
stage.
4. The blank shape (parison) is removed, rotated 180°, and transferred to
the blow (finishing) mould.
5. This mould is in two halves, made from fine-grain cast iron, and is highly
polished.
6. Air is blown into the hot parison to expand it tightly against the mould
walls.
7. The mould opens, the bottle is removed, annealed in the lehr, inspected
42
and tested, and shipped for filling.
1. A gob of hot glass drops into the blank (parison) mould.
2. The end is sealed and a puff of air pushes glass into the neck (finish).
3. A puff of air from below pushes glass into the mould and shapes it into
a ‘blank’ or parison, a thick-walled bottle looking vaguely like the final
bottle shape.
4. The blank shape (parison) is removed, rotated 180°, and transferred to
the blow (finishing) mould.
5. This mould is in two halves, made from fine-grain cast iron, and is
highly polished.
6. Air is blown into the hot parison to expand it tightly against the mould
walls.
7. The mould opens, the bottle is removed, annealed in the lehr, inspected
and tested, and shipped for filling. 43
Casting

If molten glass is sufficiently fluid, it can be poured into a

mold.
Relatively massive objects, such as astronomical lenses
and mirrors, are made by this method.
After cooling and solidifying, the piece must be finished by
lapping and polishing.
Casting of glass is not often used except for special jobs.
Smaller lenses are usually made by pressing.

44
Shaping of Flat and Tubular Glass
❖ Processes for producing flat glass such as sheet and plate glass:

Rolling of Flat Plate

Starting glass from melting furnace is squeezed through
opposing rolls whose gap determines sheet thickness, followed
by grinding and polishing for parallelism and smoothness

45
Float Process

Molten glass flows onto the surface of a molten tin bath,

where it spreads evenly across the surface, achieving a
uniform thickness and smoothness - no grinding or
polishing is needed.

46
Danner Process

Molten glass flows around a rotating hollow mandrel

through which air is blown while the glass is drawn.

47
 Forming of Glass Fibers
Glass fiber products can be divided into two categories, with
different production methods for each:

1. Fibrous glass for thermal insulation,

acoustical insulation, and air filtration, in
which the fibers are in a random, wool-
like condition. Centrifugal spraying

2. Long continuous filaments suitable for

fiber reinforced plastics, yarns, fabrics,
and fiber optics. Drawing

48
 Heat Treatment
➢ Annealing of Glass

Heating to elevated temperature and holding for a time to eliminate

stresses and temperature gradients; then slow cooling to suppress
stress formation, followed by more rapid cooling to room
temperature. Annealing temperatures are around 500°C.

➢ Tempering of Glass

Heating to a temperature somewhat above annealing temperature

into the plastic range, followed by quenching of surfaces, usually by
air jets. When the surfaces cool, they contract and harden while
interior is still plastic. As the internal glass cools, it contracts,
putting the hard surfaces in compression. Tempered glass is more
resistant to scratching and breaking due to compressive stresses
on its surfaces. 49
50