Purposes of the Course Under an English environment, the aims of this course are to introduce the history, definition and classification of fibers

Purposes of the Course Under an English environment, the aims of

this course are to introduce the history, definition and

classification of fibers to introduce the methods of fiber spinning

to students, to introduce the methods of fiber

characterization to students, and to guide students to know fiber science and

technology related persons, journals, books and companies

.

Course outline

1. Introduction 1.1 Fiber history 1.2 Fiber classification 1.3 Importance of fiber science

and technology Discussion questions and problems Bibliography

2. Fiber spinning techniques 2.1 Melt spinning

2.2 Wet spinning

2.3 Solution dry spinning

2.4 Solution wet spinning

2.5 Gel spinning

2.6 Liquid crystal spinning

2.7 Electrospinning

2.8 Bi-components spinning

2.9 Reaction spinning

2.10 Centrifugation spinning

2.11 Emulsion spinning

2.12 Interfacial polycondensation spinning

2.13 Laser associated spinning

2.14 Coaxial spinning2.15 Dry spinning2.16 Dry jet-wet spinningDiscussion questions and

problemsBibliography

3. Fiber characterization3.1 Morphology 3.1.1 Optical

microscopy 3.1.2 SEM 3.1.3 TEM 3.1.4 AFM 3.1.5 STM3.2 Thermal properties 3.2.1 DSC 3.2.2 TG/DTG 3.2.3 DMA3.3 Mechanical properties 3.3.1 Tensile 3.3.2 Elongation

3.3.3 Modulus3.4 Structure 3.4.1 XRD 3.4.2 FTIR 3.4.3 FT-Raman 3.4.4 NMR 3.4.5 UV3.5 Bio-properties3.6 Nano-propertiesDiscussion questions and

problemsBibliography

4. Materials-based fiber spinning techniques

4.1 Synthetic polymer fibers

4.1.1 PA

4.1.2 PAN

4.1.3 PP

4.1.4 PET/PBT/PTT

4.1.5 PU

4.1.6 PVA

4.1.7 PVC

4.1.8 PTFE

4.1.9 PLA

4.2 Natural polymer fibers 4.2.1 Cellulose 4.2.2 Chitin 4.2.3 Protein 4.2.4 Lignin4.3 Inorganic fibers 4.3.1 Carbon fiber 4.3.2 Silicon fiber 4.3.3 Glass fiber 4.3.4 Oxide fiberDiscussion questions and problemsBibliography

Fiber definition

Fiber is defined as a

solid materials with

stable thin shape and

long size as well as

certain level of tensile

strength.

Fiber history

1. learnt from silkworm and

2. spider since their fiber

producing process are good examples of the bio-synthetic and bio-spinning techniques because they convert non-fiber foods by enzymes into proteins in body then spun fibers as a cocoon or net.

Different fibers

Fiber from natural lotus root

The structure of the dragonfly wing leads to a development in polymer fiber with deep dark color

Bamboo fiber

Glass fiber Silicon fiber

Stone fiber

PLA fiber

Lyocell fiber

Metal fiber

Lignin fiber

Chitin fiber

Ramee fiber

Flax fiber

Spider fiber

Fiber machine and equipment

A new factory located in Malaysia

A lab. scale reactor system

1. Reactor and autoclave

a) Batch type: a unique vessel with agitator and

related heating, measuring devices usually designed to allow polymerization or dissolution materials inside. In this case, the raw materials would be charged in initially and the final product would be released finally after reaction approaching to the end.


b) Continuous type: it is usually need to arrange reactors

one after one and each plays a role only part of whole designed job. The pattern can be seen as united vessels, e.g. cascade, screw and piston flow reactor. (p174).


c) Combined type: a combination of both batch and

continuous reaction in one case.

Reactor


d) A detailed example: seeing added disk or reference

book.


e) Related elements i. Vessel: different bottoms,

e.g. flat, dished and conical

(p232) ii. Agitator: p232

1. Reactor and autoclave e) Related elements

iii. Heating device: (p232) 1. Internal: pipe spiral in vessel from top to bottom, pipe spiral at bottom of vessel, jacket. 2. Outer: pipe spiral in vessel from top

to bottom with or without jacket, only a jacket.

1. Reactor and autoclave e) Related elements

iv. Measuring device

v. Others: view hole, additives adding hole

Continuous type

Discussion problems

[1] Describing a common case where a reactor would be applied.

[2] Since agitator is of importance for

reactor, and its type seems to be varied based on polymer viscosity. Suppose a case the fluid in high viscosity, please do a selection on the basis of book.

2. Melt spinning machine and related devices (p276)

In second floor: chip charging in a hopper→through chip

gate valve→chip go to extruder(with increased temperature)→melted polymer through a filter→spinning pump→spinnerets→air quench chamber→spin finish application in quench→floor interconnection tube→to next arranged on the first floor;

2. Melt spinning machine and related devices (p276) In first floor:

→turning of the filament→winders for textile, technical or carpet year with 2-8 spin packages each→revolver winder

Or in first floor: →godets (hot or cold) with idler roller

or godet duo→BCF texturing aggregate→BCF cooling drum→filament pre-tensioning→revolver

A lab scale dual-components melt spinning machine appeared in the second floor

chip

Chip hopper

(1) Chip gate valve (p282)

A. The role of chip gate valve is to control the flow rate for chip from hopper going to next linked machine.

B. The gate valve is structured by a frame positioned on the inside of two solid plates and the spindle (shaft) sealed pressure and vacuum proof towards the outside. However, both pressure and vacuum are unable proof in detailed case.

(1) Chip gate valve (p282) C. The thickness of gate is usually of

about 2-3 mm, and controlled by hydraulic pressure. D. In addition to gate valve, ball valve is broadly used currently. However,

this valve has a problem in dead space.

Extruder

Driving system for extruder

Extruder and driving system

Chip hopper and extruder

(2) Spin extruder (pp283-284)

A. Types: Single screw extruder Double screws extruder B. Typical screw extruder (p283, Fig. 4.67) Screw and driven system C. Screw description (p284, Fig. 4.68) Different zones: feeding, transporting, compressing, metering and mixing

(2) Spin extruder (pp283-284)

D. The ratio of length to diameter, L/D, is an important parameter for understanding of screw extruder due to it in relation to detailed polymer process directly. (p286, Fig. 4.69 tabled) E. Zone length is another important

parameter for screw extruder (p289, Table 4.18)

Discussion problem

Please do a comparison of

the single and double screw

extruder.

Spinnerets after spinning

Spinnerets cleaned by oven

(3) Spinning heads and beams (p294)

A. Role of the spinning head Melting and dosing polymer fluid distribution to spinnerets. B. Types:

Discussion problem

According to p297 showed Fig. 4.84, which configuration to be the best for arrangement of spinning beams?

(4) Spinning pump (p312) Function: dosing of polymer fluid

Types: gear and piston General parameters used for describing

spinning pump (p317, Table 4.23) volume/revolution, base area, weight Materials recommended for producing

spinning pump (p314, Table 4.22)

Discussion problem

In the use of spinning pump, why people have to take care enough. Please give the reason based on book.

Discussion problem

Why a high load filtration is usually recommended?

(7) Filter (p323)

Different types (p323, Fig. 4.122 and Table

followed)

(8) Spin packs (p335)

A. the spin pack including a melt distribution filter ,distribution plate, spinneret.

B.Two loading type (i) Top loading, inserting from top (ii) Bottom loading,inserting from

bottom (iii)Inserting a spin pack is usually to

employ assistant tool as p335 indicated

(8) Spin packs (p335)

C. The pack house can be round or rectangle, but it must be designed as a pressure used to fit either high pressure on temp.

Discussion problem

Which is usually applied to inserting a spin pack?

A lifting device

or A hoist

Quench

Air system for quench

(9) Quench cabinets (p346) A. Quench description in P346

Fig 4.164 B Various quench chamber type

P348, Fig 4.165

Discussion problem

A long quench is usually for… which kind of fiber?

According to this figure (P348) presented different quench chamber types, please point out one who has the possibility for supply a fast air flow velocity?

(9) Quench cabinets (p346)

C. Relationship between the distance of spinneret &quench P349 Fig 4.167

D.Preferred quench P350 Designed by applying Laminar to

replace turbulent


E.Now quench chamber for high speed spinning (6000~12000m/min)

Please do a comparison of the difference among the common, preferred and new developed quench chambers based on this book.


F. Quench chamber accession P359

(10) Spin finish application systems (p367)

A) spin finish A 10~25% solution on emulsion in

distilled water. The concentration of spin finish for filament is thin and for stable is thick .

There are five different methods of

applying finish as can be seen in P367.

Discussion problem

Why a spinning process is usually inserted with a spin finish step?

(10) Spin finish application systems (p367) B The soil spin finish P368

It is the oldest type of spin finish, but still be applied especially to water town for speed below 1800 m/min

C. The roll spin finish P368 in addiction to roll (above

mentioned ) is only in shape.

(10) Spin finish application systems (p368)

D. Spray spin finish P368 The finish is spray on a running tow

by automating jets. E. Dipping bath as spin finish P369 The finish is placed in a pan on the

way of fiber going. Usually,the fiber is dipped in a finish bath loaded by running calendar rolls.

(10) Spin finish application systems (P368) F.spin with metering function finish P369

The spin finish process is only for application of the gear spin finish pump.

In general,the spin finish have advantages in spinning quantitatively.

Discussion problem

Of those different spin finish types , which one has been considered to have the dosing finish possibility?

(5) Spinning finish pump (p314)

Function Application place

Difference comparing to spinning pump

(6) Discharge pump and in-line pump (p315)

A. In some cases, it can be used to replace traditional screw extruder

B. In-line pump: A pipe linked pump.

Discharge pump

Discussion problem

To keep a spinning pump working as

expected in normal, which job have

to be done and this leads to do an

arrangement of which in regular?

Take-up machine

An electro-controlling system for take-up machine

Texturing machine

False twist texturing machine

A lab scale melt spinning machine

Discussion problem

Do you think it is possible for arranging a melt spinning process related machines only in one floor?

Yes, try! No, why?

(11) Spinning take-up machines (p372)

A. As above the fig of take-up machine P374. Fig 4.1972 Ⅰ. The earliest take-up machine equipped

with long friction drive rolls, which was used until above 1963. The take-up speed for the type is less than 1500m/min.

Ⅱ.The second generation of take-up machine has individually driven finish winded with speed of 8000 m/min since 1963.

(11) Spinning take-up machines (p372)

Ⅲ.A modified second generation by turned the yarn plane through 90o using mutually perpendicular godets (1972~1984)

Ⅳ.Another modified second generation with the aspect of tension controlled precision YT the take-up machine speed to be less than 3200m/min.

(11) Spinning take-up machines

Ⅴ.POY take-up machine single deck winder

double *The machine for this kind of take-up

machine is without godets. Ⅵ.Spin draw take-up machine with zone

heated godets & air-teaching separation roll with or without following high speed winder.

(11) Spinning take-up machines *For one without the high speed winders , which can be converted to for POT.

(P375.Fig.4.197) Ⅶ.A take-up machine for with the

aspect of multi-stage drawing multi-ends/positions.

Ⅷ.A take-up machine for casket your (BCF)

4 ends with a revolved winders.

Ⅸ. The multi-stove take-up machines

A. Yarn Inlet gone involve P378 inlet your guide, yarn guide often in and

for out Yarn aspiration , intermingling jet Yarn cutter , yarn sensor Yarn oils (if not in quench cabinet) B. Rolls, godets & draw roll in take-up

machine In general, they can be distinguished by

their diameter.

Dia (mm) Speed (m/min)

separator roll 12~60 <=1200

<=6000

godet 75~300 <=8000

draw roll 200~1000 <=400



C. Constructions for godet (P382)

See Fig 4.200

Polymers and related methods for fiber

spinning

PVA

3.3 polymer fiber & related machine, spanning technology

(1) Polyethylene (PE) Tm=107~138ºC

Tg=-100ºC

HDPE LLDPE

LDPE

H H C C H H

(hard ）( soft ）

(1) Polyethylene (PE)

A. Melting spinning 1965 in USA Like PP including dying condition B.Extruder: L/D ⋍ 25~30 compression ratio 1:4 small screw 1:2.5 big screw D ⋍

300mm * The best screw should be 3 zone C.Filtration is recommended


D. temp for extruder of LLDPE 135~145ºC HDPE 170 ~190ºC E. LOY: OK POY: not used yet F. Compact spinning stable PE

fiber


G. Drawing ratio for LLDPE 1:4.5~1:7.5 depending on

H. PE filament has been regarded as the softest comparing to others e.g. stable PE or all of other polymeric fibers.

MFI

melt

indexfollow

(2) Polypropylene（ PP ） P95

1958 年 Tm =169ºC

Tg=+5 ºC

only isotactic PP can be spun into fiber.

H CH3

– C – C – H H

A. Fig.2.67 P96

different ratio type of PP

atactic 无规

isotactic 全通，等规

syndiotactic 间同，反式立构，间规

Stereo block 立构规整嵌段，定向嵌段

(2)Polypropylene（ PP ）

B. Catalyst &PP type P96

Metellocene catalysts → atactic (CP2 Ti Cl2/MAO)

Cp2Ti(C6H5)MAO → isotactic C. log[]=A+BlogMFI

0.197

0.50


D. Degradation during processing (i) High sheering force in melt

cause ~ in the molecular chain

(ii) Impurities lead photo ~

E. Melt spinning of PP Fiber (filament ) (i) The phenomenon of Die swell Fig2.71

2.72 Table 2.17 Viscosity ~ temp ~ Die swell T Die swell Q Die swell Die swell do(diameter of spinneret)

Die swell (ii) crystallinity of PP filament a. start since air quench b. increase dwelling take-up c. depend on molecular weight &melt

history d. increase proportional to take-up

tension

(2)Polypropylene（ PP ） E. Melt spinning of PP Fiber

(filament ) (iii) orientation a. start since spinneret in minor b. increased with the increase of

crystallization c. i.e. after the spinneret about 60 cm d. [] orientation e. v orientation f. Q orientation g. temp orientation

(2)Polypropylene（ PP ） E. Melt spinning of PP Fiber

(filament ) （ iv ） stereo regularity Vs

crystallization Degree of crystallization, Tc


F.Aftertreatment of Polypropylene

Table P104 * That is a requirement of

understanding the relationship among the spinning methods, final filament size, shrinkage, spinneret and

take-up speed.


G. Quench for PP (P106 Fig2.82) The distance between the spinneret

should be considered based on the Fig.2.82 in page 106

H.Upwards spinning for PP 1974 England

I. electrostatic spinning of PP


J. Other spinning methods available for PP

(i) bicomponent spinning (ii) compact spinning (iii) spun bond spinning (iv) blow fiber spinning K. To heat the extruder connecting

head , the distribution pipe to each spinning position is required & recommended

(2)Polypropylene（ PP ） Take-up speed for POY-PP P106 Tab 2.19 P107 M. High tenacity PP Mv ≽150,000 narrow distribution Cv of yarn ≼790 Tscrew=230 ºC T spin head=235 ºC T spinneret=285 ºC T spin end=285 ºC Tshrowd= 160 ~ 240 º


Draw ratio 1:8 ~ 1:10 Take-up speed in water bath 50~100

m/min air quench 600 ~700

m/min chip[η] =2.5 ~3 tenacity

8.8~11g /dtex N. See picture of Fig 2.86~2.87 P109 For molding high tenacity PP

Wet quench

Air quench


O. PP proportion of the draw ratio how to influence the PP Fiber based on lecture note (P108)

(3)polyacrylonitrile (PAN) P6,111

Tm>T decomposition

Tg=0ºC(≈95ºC dry)

A. PAN fiber could be made in wet spinning with a continuous polymeringation in solution, e.g.ZnCl2/water

NH CC CH H

(3)polyacrylonitrile (PAN) P6,111

B.PAN can’t melt P113 PAN decomposer below the melting

point therefore has to be polymerized in a solvent on emulsion.

C. PAN dissolved in DMF for dry spinning

PAN dissolved in DMAc for wet spinning DMF

(3)polyacrylonitrile (PAN) P6,111 D. Table 2.21 a-b

*Problem On the basic of solvent

employment,the PAN can be obtained from two methods. Please give these methods.

E. Polymerization of PAN P115~116

(3)polyacrylonitrile (PAN) P6,111 F. The most simple installation for

precipitation polymerization of PAN is using an autoclave with a spinneret &cooling jacket. P116

G.Description of PAN polymerization Fig 2.93-2.94 P117 Fig 2.95 P118

(3)polyacrylonitrile (PAN) H. A continuous CAN polymerization

Fig 2.96 P118 J. Installation to dissolve PAN P119

①Dry spinning DMF 23~30% Wet spinning DMF ② 18~25% DMAc ① DMSO ③

T(ºC)110~140PH 6.5 ~ 9T (20 ~ 60ºC)

(3)polyacrylonitrile (PAN) J.②Dissolving temperature 40~ 60 ºC it can’t be exceed 80 ºC(P120).In order to remain the concentration of PAN.

③Dissolving vacuum usually be not in the range of 60~ 70 mbar as the same reason as before .

④After dissolving, PAN solution must be free of clumps.

⑤Dissolve = intensive stirring autoclave the mixer expect a high shear function

(3)polyacrylonitrile (PAN) K. Scale of PAN fiber production in world 7000 t/day,

25% PAN/DMF dry spinning(EU) 12% PAN/DMF wet spinning 22% PAN/DMAc wet spinning L. melt spinning of PAN P121 (Fig

2.100) PAN/DMF solution can be dry span

(3)polyacrylonitrile (PAN)

M. Description of dry spinning machine for PAN (Fig.2.100. P121)

Top: a screw drive Side: top is solution inlet bottom is a heater using

electricity After spinning: the finest is a

telescope tube that was insolated, that isa tube with electric sheathing & isolation

(3)polyacrylonitrile (PAN)

Note: At the top of the conic telescope,that has a weak around the spinneret for sucking solvent vapor.

(4) Polyvinyl chloride (PVC)

PVDC DP=800~1000 A. First PVC fiber in 1913 registered

by Klatte B. Polymerization of PVC has from

different processes P122 But for spinning PVC only the emulsion & suspension methods possible.


C. PVC particle size can be 0.01~ 0.1㎛

D. Post –chlorinating of PVC CPVC

E. The equipment for solving PVC in the same as for PAN

F. Before extrusion, PVC has to be flitted at least twice.

PVC spinning or PAN e.g. dry spinning spinning condition is like acetate wet spinning is also possible.


G.Dry spinning of PVC fiber P123 (i) Mixed with

sulfurcarbonate/acetone (France) (ii) Mixed with acetone/benzene

(Japan) H.The bath drawing PVC fiber in

water and the drawing has two stages(both in water )


I. The syndiotactic pact formed to the low temperature used in polymerization

And this leads to increase the crystalline position ,freezing temperature Tm

But the chemical resistance also be increased.


J. Synthesize PVC can be dissolved in cyclohexanon and extruded into a coagulation both of water / cyclohexanon addition solvent , ethanol or acetone

K. the washing and drawing of PVC fiber is in boiling water,drawing ratio 1:7

L. see Table 2.22 in P124

(5) Polyamide (PA)

A. Only PA6&PA66can be largely produced.

B. The number used in here present carbon number

C. Cnumber Tm for PA

D. PA6 H2N-[-HN-(-CH2)5-CO-]n-COOH spinable PA6 with n=130 ~250 P37

(5) Polyamide (PA)

E. DP=124 <rel-1> (for PA6) P40

DP=100< rel-1 > F. Polymerization of PA needs a lactam

recycling unit for economic reasons. P44 G. A description of PA6 polymerization

can be seen in P47 Fig.2.17 Polycondensation for both PA6,PA66

P58

(5) Polyamide (PA)

H.see VK-tube P48 Fig.2.18 I.spinning of PA 6 ⓐ Tm depended on final product TAb2.6 ⓑ Spinneret take-up speed increased

with the reduce of air quench cooling length for LOY, but on the constantly for POY.

P55 Tab 2.7

4. Polyvinyl chloride (PVC)

However, the individual flamed titer is the main factor for above mentioned take-up speed. P56

ⓒ Spinning condition for PA6 with various application can be seen. P57

J. Spinning of PA66 P60

(6) Polyester (PES, PET) P67

A. Spinning of PET fiber of chip with moisture small than 0.004% (P8) B.Transesterification (a) Indirect way DHT and TPA mixed with EG

(b) Direct P70 by adding glycoterephthalate

O O-(CH)2-O-C- -C-O-


C. Different between PET and PBT (a) PET

(b) PBT

The Tg =40C for PBT,that is smaller than PET e.g. 70~ 80 C (Tg) P67

O O O C C O (CH2)2

n

O O O C C O (CH2)4

n


D. Raw material for PET and a Composition

of them PMT TPA In general,the use of TPA has

advantages in increased the polymerization time, reduce cost without by product, but equipment more. P67


E. The most efficient catalysts for transes- -terificatin are acetates with Cd, Zn, or

Co. P69 F. The selection of catalytic P72 According to Fig.2.39 the increase of PET the use of catalyst seems to be sb(CH3COO)3


G. Analysis of thermo-oxidative decomposition for PET using DTA (different thermodynamics analytics) P73

H. Analysis of hydrolytic decomposition for PET using dry weighting method to be simplified.


I.The [] of PET chip relate to spinning P75

[]= [sqrt(1+1.4(rel-1))-1] /0.7

rel=1 + [](91+0.35 [])

M=(rel-1.059)104.8

= KM3.5 (K=3.6278*10-12) =ceE/RT


J . A finishes is still being used today for PET P80

K. Spinning of PET ---melt L. From finished –directly, or

continuous spinning melt velocity 4 ~ 6 cm/s in pipe,

Ø 32 ~ 100 mm, <280 C ( []= 0.6~0.7)

<290 C ([] = 0.9)


M.Take-up of PET filament P87 See formula 2.27 O. HM-HT cotton type PET staple fiber P91

[]=0.67 ~ 0.72 P. PBT 1968 P94 Tm=225 C Tg=440 C DP=100 ~

200

High modular High tenacity

(7) Polyurethanes (PU) A. Wet spinning possible DMF OR DMAc as solvent B. Dry spinning in simple and economic

P132 20 ~ 25%PU in DMF or DMAc ,with =50~150Pa S

The tube needs to keep up 140 ~ 180 C for DMF or DMAc 300 ~ 340 C for other

(7) Polyurethanes (PU) The heat zone can be managed with

two or three stages

Upper low temperature

Down high temperature

Nanofiber-based

Prof. Dr. Zhong-Lin WangGIT

A summary of different fiber spinning methods

1. Melt spinning2. Wet spinning=Solution spinning3. Gel spinning4. Liquid crystal spinning5. Bi-components spinning6. Electrospinning=electrostatic spinning 7. Reaction spinning=extruding spinning8. Interfacial polycondensation spinning9. Emulsion and suspension spinning10. Dry spinning11. Centrifugation spinning12. Laser associated spinning13. Coaxial spinning14. Assemble induced spinning

Laser associated spinning

Centrifugation spinning

Assemble induced spinning

Extruding spinning

Electrospinning

Darrell H. Reneker Department of Polymer

Science

College of Polymer Science and Polymer Engineering

University of Akron

Basic electrospinning apparatus

Tensile measurement

General Problems 1. Please describe a melt spinning route

with necessary steps. 2. Please give 20 possible names on fiber

formation. 3. Based on the textbook, an extruder is

usually designed with several areas, and please give the name of these areas and do a description briefly.

4. According to the textbook, the valve used in a spinning machine could be regarded as two types and please gives the names.

5. In which case we can find the phenomenon that defined as the dead space, please give your explanation.

6. How many pump types that you have learnt from the textbook? Please give their names and describe their relative application.

7. According to the book that the quench chamber could be designed with several types and of which one has been broadly applied in industry, please draw it on your exam paper briefly and give related reason.

8. One factory able to increase a spin finish system in the PA6 filament spinning process recently, please help it to do a selection and show related reasons.

9. Please do an outline on PA series fibers relating to their properties etc.

10. Please design possible fiber spinning route for below presented polymers:

PAN, PET, PTT, PU, PBT, PE, PP, cellulose. 11. The hair of human could be generally

regarded as a natural fiber, please describe its spinning method according to you learnt.

12. One method has been known possible for forming of a silicon fiber, please give its name and do a related description.

13. Please describe the process for rayon fiber production.

14. Please draw a picture on an autoclave with necessary parts/components.

15. Based on the fiber knowledge, please describe the formation of lotus root fiber.

Documents

Purposes of the Course Under an English environment, the aims of this course are to introduce the history, definition and classification of fibers