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ADHESIVES IN
MANUFACTURING
 MANUFACTURING ENGINEERING
AND MATERIALS PROCESSING

A Series of R e fe re n ce Books and Textbooks

S E R I E S ED I TO R S

Geoffrey Boothroyd George E. Dieter

D ep artm ent o f Mechanical Engineering Dean, College o f Engineering
University o f Massachusetts University o f M aryland
A m herst, Massachusetts College Park, M aryland

1. Computers in Manufacturing, U. Rem bold, M. Seth, and J. S.Weinstein

2. Cold Rolling of Steel, William L. Roberts
3. Strengthening of Ceramics: Treatments, Tests, and Design Applications,
H enry P. Kirchner
4. Metal Forming: The Application of Lim it Analysis, Betzalel A v itzu r
5. Improving Productivity by Classification, Coding, and Data Base
Standardization: The Key to M axim izing C A D /C A M and Group
Technology, W illiam F. Hyde
6. A utom atic Assembly, G eoffrey Boothroyd, Corrado Po/i, and Laurence
E. Murch
7. Manufacturing Engineering Processes, Leo A!ting
8. Modern Ceramic Engineering: Properties, Processing, andUse in Design,
David W. Richerson
9. Interface Technology for Com puter-Controlled Manufacturing Processes,
Ulrich Rembold, Kart Arm bruster, and Wolfgang Ulzmann
10. H ot Rolling o f Steel, W illiam L. Roberts
11. Adhesives in Manufacturing, G erald L. Schneberger

OTHER VOLUMES IN PREPARATION

ADHESIVES IN
MANUFACTURING
edited by
Gerald L. Schneberger
G M I Eng i n e e r i ng a n d M a n a g e m e n t I n s t i t ut e
Fl i nt, M i c h i g a n

M ARCEL DEKKER N e w York

Library of Congress Cataloging in Publication Data

Main entry under t itle :

Adhesives in manufacturing.

(Manufacturing engineering and materials

processing ; 1 1 )
Includes index.
1. Adhesives. I . Schneberger, Gerald L.
II. Title. III. Series.
TP968.A29 1983 668L3 83-7867
ISBN 0-8247-1894-1

COPYRIGHT © 1983 by MARCEL DEKKER ALL RIGHT RESERVED

Neither this book nor any part may be reproduced or transmitted in

any form or by any means, electronic or mechanical, including photo­
copying , microfilming, and record in g, or by any information storage
and retrieval system , without permission in writing from the publisher.

MARCEL DEKKER
270 Madison A ven u e, New York, New York 10016

Current printing (last digit) :

10 9 8 7 6 5 4 3

PRINTED IN THE UNITED STATES OF AMERICA

Preface

Adhesives in Manufacturing has been written primarily to serve pro­

duction and development people. While basic researchers may find its
contents interesting and o f va lu e, its major thrust is to provide in fo r­
mation and understanding for those who choose to use adhesives.
The chapters have been grouped to first introduce Fundamentals
and then consider Specific Types of Adhesives. These sections are
followed by chapters which consider the Techniques o f Bonding Prac­
tice and the Perform ance, Durability, and Testing o f bonds. It is
hoped this arrangement will enable readers to progress in a logical
fashion from the general to the sp ecific.
The authors chosen to prepare chapters for Adhesives in Manu­
facturing are a select group o f extremely knowledgeable persons who
represent adhesive formulators , distribu tors, and consumers. Col­
lectively they possess an immense amount o f knowledge and practical
experience. They have attempted to prepare material geared to manu­
facturing and process selection personnel—people whose knowledge of
chemistry is limited but whose need to work with chemicals is g rea t.
It is a pleasure to thank the authors for their excellent overall
attitude o f cooperation and enthusiasm during the months o f writing
and editing which preceded publication. The support and assistance
o f the sta ff at Marcel D ekker, In c . was also effective and is appreci­
ated .
F inally, it is with the greatest gratitude that the efforts of
Mrs. Mary R en sb erger, Editorial Assistant for the p roject, are recog­
nized. Without her organizational ability and conscientious attention
to detail, the endeavor would never have been brought to fru ition.
The editor would be pleased to receive comments and construc­
tive suggestions concerning Adhesives in Manufacturing at any time.

Gerald L. S chn eb erg er

Contributors

John R . Adams, B . S . , M .E .
Director of Education, Training D ivi­
sion , Binks Manufacturing* Company, Franklin P a rk , Illinois

W erner Bohm Director of Marketing, Packaging and Product Assembly

D ivision, Nordson Corporation, Atlanta, Georgia

Justin C . Bolger # S c . D . , M .S ., B . S . Vice President and General

Manager, Polymer Products D ivision, Amicon Corporation, Lexington,
Massachusetts

Donald H . B u c k le y , D . E n g . , D . J u r is ., B . S . Chief, Tribology

B ranch, National Aeronautics and Space Administration Lewis Research
C enter, C leveland, Ohio

R ichard C h a it , P.E . , B .S ., M .S ., Ph.D . Chief, Materials In tegrity

and Testing Technology Division, Army Materials and Mechanics R e­
search Center, Watertown, Massachusetts

Edward T . C legg, A . B ., M .B . A . Chemist, Engineering Standardiza­

tion Branch, Army Materials and Mechanics Research Center, Water­
town , Massachusetts

Garry O . DeFrayne, B .S ., C h .E ., M .A. Senior Materials E ngineer,

Adhesives Laboratory, Chrysler Corporation, Highland Park, Michigan

R obert D . D exheim er, B . A . * Market Manager, Henkel Adhesives

Company, Minneapolis, Minnesota

Business Manager, Adhesives D ivision ,

James A . Graham , B . A .
Chemical Product Group, Lord Corporation, E rie, Pennsylvania

*Retired

v
vi C o n trib u tors

J . W. H agan, B .S . Senior Development Scientist, Specialty Chemi­

cals Division, Union Carbide Corporation, Bound B rook, New Jersey

M artin H auser, B . S . , Ph. D .

Vice President, Environmental Health
and Safety, Industrial Group, Loctite Corporation, Newington,
Connecticut

Manager, Product Engineering,

G ira rd S. H avila n d , C M fgE , B .M E .
Loctite Corporation, Newington, Connecticut

B a rry R . K illic k , B .S .A .e . Chief Engineer, Pyles D ivision, Kent-

Moore Corporation, Wixom, Michigan

Harold K oski, A .B ., M .A .* Associate Professor o f Chemistry,

Department of Science and Mathematics, GMI Engineering and Manage­
ment Institute, F lin t, Michigan

Jan V . L in d y b e rg , B .S ., M .S .
Technical Marketing Specialist, RTV
Products Department, General Electric Company, Silicone Products
Division, W aterford, New York

Gregory M. M acIver, B .S ., Ch.E. Product Sales Manager, Adhesives

Operations, Chemical Division, Goodyear Tire and Rubber Company,
Ashland, Ohio

Dale M einhold, B .S ., M .S . Associate Professor of Mathematics,

Department of Science and Mathematics, GMI Engineering and Manage­
ment Institu te, F lin t, Michigan

J . Dean M in fo rd , B . S ., M. L i t t ., Ph. D.
Scientific Associate, Product
and Process Engineering Division, Alcoa Laboratories, Alcoa Center,
Pennsylvania

J . Merle N ielsen, B .S ., M . S ., Ph. D .

Materials Engineer, Materials
Information S ervices, Corporate Research and Development, General
Electric Company, Schenectady, New York

Paul 0 . N ielsen, B .S. President, Paul O . Nielsen, Inc. , Warren,

Pennsylvania

W. A. Pletcher, B .S ., M .S ., P h .D . Laboratory Manager, Industrial

Products Laboratory, A dhesives, Coatings and Sealers D ivision, 3M
Company, S t. Paul, Minnesota

^Retired
C o n trib u tors vii

Gerald L. Schneberger, P .E ., A .B ., M .S ., Ph.D. D irector, Contin­

uing Education and Professional S ervices, GMI Engineering and
Management Institute, F lin t, Michigan

Kenneth C . S tu eben , P h .D . Senior Research Scientist, Specialty

Chemicals Division, Union Carbide Corporation, Bound Brook, New
Jersey

J. M. T a n c re d e , P h . D . * Project Scientist, Coatings Materials D ivi­

sion, Union Carbide Corporation, Bound Brook, New Jersey

Douglas P. Thom pson, 11, B .S . Sales Engineer, Adhesives Opera­

tions , Chemical Division, Goodyear Tire and Rubber Company, Ash­
land, Ohio

Technical Representative, Technical

William F. Thomsen, B . S . , M .A .
Service and Development Division, Eastman Chemical Products, Inc. ,
K in gsport, Tennessee

Leonard R . V e rtn ik , B .S . Manager o f Technical Services, Henkel

Adhesives Company, Minneapolis, Minnesota

William K . W estray, P .E ., B . S . , M .S . f Marketing Manager, Magnus

Metal Processing Division, Economics Laboratory, Inc. , St. Paul,
Minnesota

Edmund J. Y aro c h , B .C h E .
Laboratory Manager, Automotive, Con­
struction and Convenience Packaging Products Laboratory, A dhesives,
Coatings and Sealers Division, 3M Company, St. Paul, Minnesota

R obert H . Y o u n g , Ph. D . , M .S c . , B .S c . $ Group Leader, Research

and Development, Union Carbide Corporation, Bound Brook, New
Jersey

Present affiliations
♦Senior Research Chemist, Specialties Technology D ivision, Exxon
Chemical Company, Baton R ouge, Louisiana
fMarketing D irector, Barnes Drill Company, R ockford, Illinois
$ Section Leader, Research and Development, Weyerhaeuser Company,
Tacoma, Washington
Contents

Preface
C o n trib u to rs

F UN DA M E N TA LS

1. Adhesive Concepts and Term inology

Gerald L. Schneberger

2. Surfaces
Donald H. Buckley

3. Polymer S tru c tu re and A dhesive B ehavior

Gerald L. Schneberger

4. D esigning A dhesive Joints

Gerald L. Schneberger

5. S electing an A d h e s iv e : Why and How

Paul O. Nielsen

6. Hazardous M a te ria ls —An O verv ie w

J. Merle Nielsen

TYPES OF A DH ESIVES

7. S tru c tu ra l A d h e s iv e s : T od ay's S tate o f the A rt

Justin C. Bolger

8. U reth an e S tru c tu ra l A dhesive Systems

Gregory M. Maclver and Douglas P. Thompson, I I
X Contents

9. Modified A c ry lic S tru c tu ra l Adhesives 209

James A . Graham

10. Phenolic A dhesives and M odifiers 237

Robert H. Young and J. M. Tancrede

11. Anaerobic A dhesives 269

Martin Hauser and Girard S. Haviland

12. C yano acrylate A dhesives 305

William F. Thomsen

13. H ot-M elt Adhesives 325

Robert D. Dexheimer and Leonard R. Vertnik

14. P re s s u re -S e n s itiv e Adhesives 353

J. W. Hagan and Kenneth C. Stueben

15. R T V Silicone A dhesive Sealants 387

Jan V . Lindyberg

16. W ater-Based A dhesives 407

W. A. Pletcher and Edmund J. Yaroch

BONDING P R A C T IC E

17. Metal Cleaning 427

William K. Westray

18. S p rayin g Adhesives 439

John R. Adams

19. D ispensing H ig h -V is c o s ity A dhesives and Sealants 471

Barry R. Killick

20. H ot-M elt A pplication Equipm ent 499

Werner Bohm

21. A dhesives fo r Specific S u b strates 525

Gerald L. Schneberger
Contents xi

PERFORMANCE, D U R A B I L I T Y , A ND T E S T IN G

22. T e s tin g Adhesives 551

Harold Koski and Gerald L. Schneberger

23. Permanence o f A dh esive-B o n ded Aluminum Joints 567

J. Dean Minford

24. Mathematical Modeling and S tatistical In ference 603

Dale Meinhold

25. A dhesive S pecifications and Q u a lity C ontrol 635

Garry 0. DeFrayne

26. Adhesives and the S ta n d a rd iza tio n Program Within the 649
D epartm ent o f Defense (D O D )
Richard Chait and Edward T. Clegg

In d ex 671
FUNDAMENTALS
 1
Adhesive Concepts and Terminology

Gerald L. S chn eb erg er GMI Engineering and Management Institute,

Flint, Michigan

I. Introduction 4
II. Surfaces 4
III. Adhesion 5
IV. Wetting* 5
V. Bond Strength 5
V I. Fatigue Life 6
V II. Heat Limitations 6
V III. Debonding 6
IX. Unstressed A gin g Data 6

X. Nondestructive Testing 7
X I. Expansion Coefficients 7
X II. Creep 7
X III. Thermoplastic 8

XIV. Thermosetting 8
XV. Surface Conversion 8
XVI. Scanning Electron Microscopy
X V II. Pot Life 8
X V III. Viscosity 9
XIX. Thixotropy 9
XX. Glass Transition Temperature
XXI. Shelf Life 9
X X II. Curing 9
X X III. Sag Resistance 10
XXIV. Resin 10
XXV. Polymer 10
XXVI. Mold Release Agent 10
XXVII. Outgassing 10
X X V III. Curing Agent 11
XXIX. Hardener 11
XXX. Filler 11
XXXI. Adhesive Failure 11
XXXII. Cohesive Failure 11

3
4 Schneberger

I. IN T R O D U C T IO N

A knowledge of basic concepts and terminology is helpful in deriving

the maximum benefit from the use of adhesives and facilitating com­
munication between designers , u sers, and producers. This chapter,
th erefo re, contains a b rie f description of the more important terms and
ideas involved in bonding. They are arranged in no particular order
of significance and many of them are described or discussed in fu r ­
ther detail in other chapters of the book.

II. SURFACES
Surfaces are complex and dynamic. They are never flat despite the
best attempts at polishing. Industrially bonded surfaces often have a
surface roughness of 50—100 microinches (12,700—25,400 ym) or more.
Rough surfaces are neither automatically good nor bad for bond­
ing. The smoother the su rface, the fewer crevices and microvoids are
present to retain trapped air and prevent good contact of the adhe­
sive with the su rface. On the other hand, a rough surface provides
more actual surface area for contact with the adhesive and may even
allow some mechanical interlocking as the adhesive solidifies in cracks
and crevices.
The most important property o f a su rface, as far as bonding is
concerned, is cleanliness. Unless surfaces are clean , that i s , free of
loosely held foreign material, the bond may fail unexpectedly and/or
at low loads for no apparent reason. Typical surface contaminants
include d ir t , o il, grease, mold release, oxid es, moisture, gases , and
lubricants.
Surfaces are dynamic in the sense that their chemical composition
is frequently subject to change with time. Some metals may oxidize
(corrode) by reacting with atmospheric moisture and oxygen which
permeate the bondline. Occasionally, plastic surfaces may become
coated with chemicals that migrate from the interior of the part or
which reach the surface from the external atmosphere by diffusion
through the bondline. In either case, a competition for attachment to
the surface develops between the adhesive and the newly arrived
chemical. Strong, long-lasting adhesives are generally those whose
chemical structure is such that they can compete favorably for surface
attachment sites with other chemicals which may find their way to the
surface.
Surfaces also have a different composition than might ordinarily
be expected. Most commonly, bonded metal surfaces e x is t, not as free
metals, but as hydrated metal oxid es. Freshly milled aluminum su r­
faces , for example, begin forming a transparent oxide layer immedi­
ately when exposed to the atmosphere. Iron and ferrous alloys do
likewise. Applying adhesives to a metal-oxide surface is not neces­
sarily bad. I f the metal oxide is tigh tly bound to the metal and is co­
Adhesive Concepts and Terminology 5

hesively strong and chemically stable, then the resulting adhesive

bond may be both strong and durable. Aluminum, for example, is
frequently oxidized under strictly controlled conditions (anodized)
prior to bonding in order to provide the type o f surface just describ­
ed.

III. ADHESION

Adhesion is the phenomenon which allows two objects to retain surface

contact nonmagnetic a lly . Most theories of adhesion can be expressed
in terms of electrical attractions. Essentially, certain minute locations
on one surface possess or acquire positive or negative electrical
charges which then align themselves adjacent to an oppositely charged
location on the other surface. The ensuing unlike charge attractions
result in adhesion of the surfaces. An adhesive is simply a material
applied as a liq u id , which allows the establishment o f unlike charge at­
tractions and then solidifies to provide the bond with significant in te r­
nal strength.

IV . W ETTING

Wetting refers to the ability of a liquid to intimately contact the sur­

face over which it flows. Poor wetting is typified by water on a waxed
surface. The water has a tendency to "bead up" because the water
molecules are more vigorously attracted to themselves than they are to
the waxed surface. Good wetting is essential for strong adhesive
bonds. Adhesives may contain wetting agen ts, that i s , chemicals
which increase the ability of the adhesive to contact and be attracted
to the surfaces being bonded. Wax, grea se, oil, and fluorocarbons
are notoriously difficult to wet. It is for this reason that most sur­
faces are subjected to some sort of degreasing treatment prior to bond­
ing.
Surfaces which are not easily wet by water will be difficult to
bond. The "water-break free" test is often used to determine the
bondability of surfaces. Water is poured on the surface and observed
to see whether it breaks up into droplets or remains as a single pud­
dle. I f individual droplets are form ed, the surface is presumed to be
contaminated with grease or oil. Some fluorocarbons, hydrocarbons,
and silicones can not be wet by water even when they are clean. The
test works well for nearly everyth ing e ls e , how ever.

V. BOND STR ENG TH

Bond strength refers to the amount of force required to break the

bond. It represents the force required to overcome either the adhe-
6 S c h n e b e rg e r

sive strength o f the bond or the cohesive strength of the adhesive

material or of one o f the bonded objects.

VI. F A T IG U E LIFE

Fatigue life , which is usually expressed as the number o f cycles r e ­

quired for fa ilu re, is the number of times a stress can be applied and
released before the bond fa ils. The test is usually performed with an
electrically driven instrument capable of subjecting the bond to tension
or bending at a v e ry high frequ en cy. The underlying assumption is
that the harmful effect o f such stresses will be cumulative, and al­
though they are performed at a v e ry high frequency, it will still be
possible to correlate the results with service conditions.

V II. HEAT L I M IT A T I O N S

Most structural adhesives begin to lose strength significantly at tem­

peratures above 300°F ( 149°C). A few are available which can tolerate
continuous exposure at 400°F (204°C) or h igh er. The basic difficulty
experienced by most adhesives at high temperatures is simply that the
chemical bonds which are an inherent part o f their structure begin to
break down as the temperature increases. In va riab ly, those products
which have extremely high heat stability also contain chemical bonds
of unusual thermal stability. Sometimes heat-stable fillers can be add­
ed to the formulation in order to raise the service temperature.

V III. DEBONDIN G
Debonding is the process by which an adhesive looses its attachment
to a su rface. Debonding usually occurs when water or some other
chemical displaces the adhesive from surface attachment sites. The
process is usually a gradual one although it may not be noticed until
the adhesive and the adherend separate completely, and a catastroph­
ic failure resu lts.

IX . UNSTRESSED AG ING D A T A

Unstressed aging data describe how bond properties of interest, pos­

sibly impact or shear stren gth , change with time using specimens that
have not been stressed prior to testing. Engineers frequently request
that strength-retention data be collected for a particular adhesive
bonding system. As a result, bonds are made and tested to failure at
various times after joining. The results obtained frequently depend
heavily upon whether the samples were simply stored under ambient
Adhesive Concepts and Terminology 7

conditions or whether they were cyclically stressed before testing.

Since most adhesively bonded products will experience stresses in
se rv ic e , it is often misleading to base any decision concerning them
on test results obtained from unstressed samples.

X. N O N D E S T R U C T IV E T E S T IN G

Nondestructive testing refers to a number o f tests for bond strength

or durability which are performed on assemblies without destroying
the bond. Nondestructive tests are often carried out by subjecting
the bond to ultrasonic vibration or other physical stimuli and measur­
ing the physical response o f the system. Techniques range in com­
plexity from a hammer-tap sound test to electronic frequency analysis.

XL EXPANSION C O E F F IC IE N T S

The expansion coefficient o f a material is a number which indicates

how the material changes dimensionally with changes in temperature.
An expansion coefficient of 6 x 1 0 " ^ cm/cm/°C means that a 1-cm se g ­
ment will increase 6 x 1 0 " ^ cm in length for each degree Celsius o f in ­
creased temperature. Similarly the part will shrink by the same
amount for each degree o f temperature decrease. This concept is im­
portant in adhesive bonding because adhesives are frequently used to
join materials with dissimilar expansion behaviors. Furthermore, the
adhesive itself undergoes expansion and contraction as the tempera­
ture rises and fa lls. When the mismatch of expansion behavior is too
g rea t, severe stresses result at the bondline, and a separation or
fracture o f the adhesive may occur. Increasing the flexibility of the
adhesive is a common technique for resisting expansion - contraction
failu re. In general, flexible adhesives are better able to resist such
stresses because they can shrink and stretch with the moving ad-
herends. On the other hand, flexible formulations often have a great­
er tendency to creep. The expansion behavior of adhesives can often
be modified by the addition of fillers or additives.

XII. CREEP
The tendency of any material to undergo a permanent change in di­
mension when subjected to mechanical stress is known as cre ep .
Creep is particularly a problem with thermoplastic polymers. The ten ­
dency of a material to creep results primarily from the flexibility of its
molecular segments. Creep may often be retarded or reduced to an
acceptable level with fillers or small amounts o f crosslinking.
8 Schneberger

X III. T H E R M O P LA S T IC

Polymers which soften when heated are called thermoplastic. With

ve ry few exceptions, they are also soluble in at least a few solvents.
Thermoplastic materials usually have a tendency to creep under load,
and they are generally not used for critical structural application.

X IV . T H E R M O S E TT IN G

Plastics which do not deform readily under load and which resist solu­
tion in nearly all solvents are called thermosetting. The molecular
chain segments of thermosetting materials are chemically bound to one
another (crosslinked) in such a fashion that it is difficult for segments
to move independently. In e ffe c t, the chain segments lock each other
in place, and permanent deformation is difficult or impossible at ord i­
nary temperatures. Solvents are also unable to dissolve thermosetting
resins.

XV. SURFACE CONVERSION

Surface conversion refers to any process in which the surface to be

bonded is changed from its condition as manufactured or assembled to
one which is more suitable for bonding. More than simple cleaning is
implied by surface conversion. T yp ica lly , a ferrous surface might be
converted to zinc phosphate, or an aluminum surface to aluminum
oxide. Phosphatizing, anodizing, chromating, and polymer oxidation
are typical o f conversion processes widely used industrially. The ad­
vantage of surface conversion is simply that the surface is changed
from a more or less unknown condition to one of fairly well understood
composition and behavior. T h u s, some assurance is gained that the
adhesive is always being applied to a uniform surface.

X V I. S C A N N IN G ELECTRON MICROSCOPY

This is a surface observation technique using a microscope which de­

pends upon electron beams rather than light rays for magnification.
It gives extremely high magnifications with excellent depth of fie ld .
Magnification up to 100,000 or more are achieved with relative ease.
The equipment is expensive and somewhat sophisticated, but its ac­
quisition may be justified in certain critical situations.

X V I I . POT LIFE

The period of time after mixing a two- or three-component adhesive

during which the mixture is still workable is the pot life. Once the
Adhesive Concepts and Terminology 9

pot life has been exceeded, the viscosity of the formulation becomes
so great that spreading and wetting is d ifficu lt.

XVIII. V IS C O S IT Y
Viscosity is the ability of a liquid to resist flow . In practical term s,
solutions o f high viscosity are difficult to stir, pump, and spray.
Low-viscosity formulations, on the other hand, may be excessively
runny and difficult to apply uniformly to vertical surfaces. This
problem is often solved through the addition o f thixotropic materials.

X IX . T H IX O T R O P Y
A temporary decrease in viscosity upon stirrin g is called th ixotropy.
In more technical term s, it is accurate to say that the viscosity of
thixotropic materials is shear-rate dependent. Thixotropic additives
are often used to give an adhesive enough body to resist sagging on
vertical surfaces and yet become runny enough to flow easily under
the stress of brushing, rolling, or spraying during application.

XX. GLASS TRANSITION TEMPERATURE

The glass transition temperature T g is the temperature above which an
adhesive (o r other polymeric material) becomes somewhat ru b b ery . At
temperatures above the T g , polymers are somewhat ductile while at
temperatures far below the transition poin t, they are often brittle.
Adhesive formulators generally select resins having transition temper­
atures which are a compromise between flexible-ru bbery and brittle-
glassy structures. Adhesives designed for use on flexible materials
almost always have transition temperatures below the anticipated use
temperature to insure that the bondline will remain flexible in service.

XXL SHELF LIFE

Shelf life is the period of time for which an adhesive may be stored
without deteriorating to the point that performance will be unsatisfac­
tory. Shelf life for reactive adhesives can usually be extended by
refrigeration.

X X II. CURING
Curing is the process during which an adhesive changes from a liquid
to a solid. Classically, curing means the formation of a crosslinked
polymer film. More loosely, the term is sometimes used to describe
10 S c h n e b e rg e r

any method of forming a solid adhesive film , including solvent loss and
linear polymerization.

XXIIL SAG RESI STANCE

Sag resistance refers to the ability o f the adhesive to stay in place on

a vertical surface without running or ’’sagging" on the surface. Fill­
ers are sometimes added to adhesives to give them more body and im­
prove their sag resistance.

XXI Ve RESIN

The major polymer or polymer - for min g material used in an adhesive is

the resin . Some resins are natural products such as starch or rubber.
Other resin s, such as epoxies and urethanes, are produced by chemi­
cal synthesis.

XXV. POLYMER
The plastic-like material which forms the bulk o f most adhesive films is
a polymer. Polymers are made by the repetitive joining o f many small
chemical units (m olecules). The resulting high molecular weight ma­
terial is known as a polym er. Most o f the bulk properties of an adhe­
sive material, such as heat resistance and tensile strength, are p r i­
marily due to the nature o f the polymer used in the adhesive.

XXVI. MOLD RELEASE AGENT

Mold release agents are materials used to reduce the adhesion o f a

polymer to the mold in which parts are form ed. Release agents are the
opposite of adhesives. Their task is to reduce or prevent adhesion.
Release agents may either be applied to a mold surface before it is fill­
ed (external release agents) or mixed into the molding material before
it is used (internal release a g e n ts ). In either case, it is essential that
mold release agents be removed from surfaces before bonding is at­
tempted.

XXVII. OUTGASSI NG
Outgassing is the formation of gas bubbles in an adhesive film while it
is curing. This generally undesirable situation may arise because
gaseous products are formed while the adhesive cures or because cur­
ing conditions, such as temperature, may cause bubbles o f dissolved
air to be released. In general, severe outgassing should be avoided.
Adhesive Concepts and Terminology 11

XXVIII. C UR IN G A G E NT
Curing agents are chemicals which react with an adhesive to form a
solid adhesive film . Curing agents are generally used in much larger
amounts than catalysts. They may be considered coreactants with the
adhesive resin since they are consumed during the curing reaction.

X X IX . HARDENER

Hardener is a term which is more or less synonymous with catalyst.

Hardeners are mixed with adhesive resins in v e ry small quantities to
initiate the curing reaction.

XXX. F IL L E R

A material which is added to an adhesive formulation to influence its

properties in some specific fashion is called a fille r . Fillers are gen­
erally particulate materials, such as finely ground glass, metal, clay,
or other inorganic chemicals. They are used to control such proper­
ties as impact resistance, heat sta b ility, condu ctivity, sag resistance,
e tc .

X X X I. A D H E SIVE F A IL U R E

Adhesive failure is the failure of a bond at the interface between the

adhesive and the adherend.

X X X II. COHESIVE F A ILU R E

The failure o f a bond within either the adhesive or the adherend,

rather than at the interface between them, is known as cohesive fail­
ure.
 2
Surfaces

Donald H . B uckley National Aeronautics and Space Administration

Lewis Research Center, Cleveland, Ohio

I . Introduction 13
I I . Surface Profile 14
I I I . Crystalline Structure 19
IV. Chemistry of Surfaces 21
A . Chemisorption 26
B . Compound formation 27
C . Metallurgical effects 28
V. Surface Film Effects 29
V I . Characterization o f Surfaces 31
A . Microscopy 31
B . Etching 32
C . Analytical surface tools 33
D. Adhesion 44
References 49

h IN T R O D U C T IO N

When a solid surface is examined either microscopically with a scan­

ning electron microscope or mechanically with a surface profilom eter,
it is found to contain irregu la rities; that i s , the surface is not flat and
smooth. A depiction of a surface displaying these irregu la rities, or
asperities as they are commonly called, is presented in Fig. la.
Nearly all real surfaces contain the asperities except brittle,
single-crystal materials that have been cleaved along natural cleavage
planes and metallic pin tips that have been field evaporated in the
field ion microscope. Even with brittle materials, the cleavage pro­
cess results in the generation of surfaces that contain cleavage step s,
and it is only the terraces between these steps that are atomically
smooth.
The actual shape and distribution of surface asperities has been
the object of considerable research. An excellent review of the sub­
ject can be found in Williamson [ 1] .

13
14 Buckley

The surfaces of the asperities are not atomically clean but contain
surface films (F ig . l b ) . For metals and alloys these films generally
consist of oxides and adsorbed gases— usually water va p o r, carbon
monoxide, and carbon dioxide. With many nonmetals the surface films
may simply consist o f other adsorbates. All o f the reacted and ad­
sorbed film materials can exert a strong effect on the mechanical and
metallurgical behavior of the solids to which they adhere, as indicated
by the collection of papers appearing in Westwood and Stoloff [2] .
In addition to the films present on the surface of a solid, the
surficial (near surface) layers of the solid itself may vary consider­
ably in structure from the bulk of the solid. With crystalline solids
these layers may consist of recrystallized material, strain hardened
region s, and/or textured region s. These surficial layers develop
when any type of finishing or polishing of the surface is done, par­
ticularly when that surface is a metal. These layers can also be a re ­
gion rich in bulk impurities [ 3] . In amorphous solids these layers may
contain voids and microcracks.

II. SURFACE PROFILE

A careful examination of industrially prepared metal and alloy surfaces

with surface profilometers (devices capable of revealing the surface
topography) indicates the true microroughness of these surfaces.
They are, on a microscale, rough— as indicated by the surface p ro­
file traces of Fig. 2. The surface represented by Fig. 2a, steel fin i­
shed by mechanical wire brushing, is extremely rough and contains
many large irregu la rities. The surface of Fig. 2b, steel prepared by
conventional industrial grinding, is much smoother, but many micro­
irregularities still exist. When a steel surface is ve ry carefully lap­
ped, smaller and fewer asperities are produced. This is demonstrated
in the surface profile trace of Fig. 2c, the smoothest of the three
Surfaces 15

(b) Ground

(c) Lapped

Fi g. 2. Profiles of steel surfaces finished by three different methods,

(a ) Brushed; (b ) ground; (c ) lapped.

traces presented. Even the lapping, however, leaves some surface

roughness.
Extremely smooth, asperity-free surfaces are shown in the profile
traces o f Fig. 3a and b for mica and quartz surfaces. Both surfaces
were generated by cleavage. A crack which developed during the
cleavage process is visible in the profile trace of the mica surface.
Normally, metal surfaces cannot be generated with the smooth­
es s reflected in the profiles o f Fig. 3a and b. Such surfaces can be
generated in the field ion microscope, but this only provides an atom­
ically smooth surface over an area reflected by the pin tip radius of
500—1000 A. Deposition of metal films on quartz surfaces as that in
Fig. 3c can be used to obtain an asperity-free metal surface. The r e ­
sults o f such an approach are shown in the surface profile trace o f Fig.
3d for iron vapor deposited in vacuum onto quartz. The surface is
smooth compared to those in Fig. 2.
Very frequently, for example, when a greater surface area would
promote such things as adhesion, it is desirable not to have extremely
smooth surfaces. A host of different methods — mechanical, chemical,
and physical— can be used to increase surface area.
16 Buckley

(a)

(b)

(c)

<d)

F ig . 3. Surface profiles of various materials. (a ) Mica; (b ) qu a rtz;

(c ) iron on quartz; (d ) 1 . 0 -ym standard surface roughness.

One of the most commonly used mechanical methods is to sand or

bead blast the surface, thereby removing material through erosive
wear. An example of such a surface is shown in the photomicrograph
of Fig. 4. The surface looks like waves on water. This kind of sur­
face topography may be ve ry useful in certain bonding applications,
catalysis, and chemical processes.
Among the chemical surface-roughening methods, chemical etch­
ing isL used. The particular reagents must be selected on the basis of
the surface to be etched.
Surfaces 17

F ig . 4. Photomicrograph of a glass-bead blasted aluminum surface.

1 cm = 0 . 0 1 mm.

A ve ry good technique for the roughening o f surfaces involves

the use of inert gas ions which are made to bombard a surface and
generate a surface texture. Ion etching, as it is called, is particular­
ly versatile in that both the bombarding species and the ion energies
can be selected to vary the surface topography. In addition, the in ­
cident angle o f the ion beam can be varied. The different types of
surface textures that can be developed by this technique are indicated
in the photomicrographs o f silver surfaces shown in Fig. 5. In the
upper portion of the figure the various surface orientations are de­
picted on the unit triangle. In the three micrographs in the lower
portion of the figu res, the ion etching effect on three principal planes
o f silv er—namely, the ( 1 0 0 ) , ( 1 1 0 ) , and ( 1 1 1 ) surfaces— are shown.
The photomicrographs of Fig. 5 indicate that considerable variation in
surface texture can be developed with ion beam etching.
 18
B u c k le y

{100} *1 no I {III}

Fig. 5. Ion beam etched silver crystal surfaces with normally incident
A r + at 8 k e V ; dose 7 x 1018 ions.
Surfaces 19

III. C R Y S T A L L IN E S T R U C T U R E

The crystal structure of ideal surfaces for most practically used ma­
terials is generally one of three major ty p e s : body-centered cubic,
face-centered cu bic, or close-packed hexagonal. All engineering
surfaces vary from these ideal structu res. Most real surfaces have
grain boundaries which develop during the solidification of crystal­
line solids. These grain boundaries are, in a strict sense, defects
which exist in the bulk solid and extend to the surface. They are
atomic bridges linking the crystal structure of the two adjacent grains.
Because of their role they do not possess a regular stru ctu re; they
are highly active and are ve ry en ergetic. Grain boundaries are large
d efects, readily observable on real surfaces. In addition to these
there a re , however, many lesser defects that may ex ist. These in ­
clude subboundaries , twins , dislocations, interstitials , and vacancies.
Subboundaries are low-angle grain boundaries where only a
slight mismatch in the orientation of adjacent grains occurs. When the
crystal lattices of the adjacent grains are not parallel but are slightly
tilted one toward the o th er, the defect is referred to as a tilt bound­
ary . When the lattices are parallel, but one is rotated about a simple
erystallographie axis relative to the other with the boundary being
normal to this a xis, the defect is a twist boundary.
The twin boundary occurs where there is only a degree or two o f
mismatch between the twins with the twins being mirror images of each
other. They are frequently seen on the basal planes o f hexagonal
metals with deformation.
Dislocations are atomic line defects existing in crystalline solids.
They may actually be in the subsurface and terminate with one end at
the surface or they may be in the surface. There are those disloca­
tions that are entirely along a line where an extra half plane o f atoms
exists; these are called edge dislocations. In addition, there are
screw dislocations that form along a spiral dislocation line. A screw
dislocation can be seen on the surface as a wedge of atoms which is
the terminus of the spiral. The small-angle boundaries or subbounda­
ries referred to earlier are generally composed of edge dislocations.
It is the presence of these defects which cause crystalline solids to
deviate so markedly from theoretical strength.
Some of the crystalline defects that may be found on a solid su r­
face are presented schematically in Fig. 6 . The vacant lattice site
(F ig . 6 a) is simply the absence of one atom from a crystal lattice site.
The interstitial (also shown in Fig. 6 a) is an extra atom crowded into
the crystal lattice. Edge and screw dislocations are shown in Fig. 6 b,
and the small-angle boundary in Fig. 6 c.
Mechanically finished surfaces generally have undergone a high
degree o f strain and thus may contain a large amount o f lattice dis­
tortion which generates high concentrations of dislocations. While the
initial presence of dislocations causes a reduction in strength, their
 Buckley

o o o o
o o o o
(a)

(b)

(c)

F ig . 6. Crystalline defects in solids. (a ) Vacancy and interstitial

crystal defects. (b ) Edge and screw dislocations. (c ) Small-angle
boundary composed of edge dislocations indicated by T symbols.

multiplication and interaction during deformation produces an increase

in surficial strength.
With plastic deformation of real surfaces, the strain produces a
reduction, generally, o f the recrystallization temperature of the ma­
terial at the surface. In many materials the combination of strain and
temperature can bring about surface recrystallization, which has an
annealing effect. Annealing relieves the lattice strain and the stored
e n e rg y ; a sharp reduction in the concentration o f surface defects r e ­
sults. In a dynamic, nonequilibrium system , such as that encounter­
ed in mechanical activity on su rfaces, the surface layers may be
strained many times, recrysta llized , and then strained again.
Surfaces 21

F ig . 7. Lattice distortion under compressed surface stress.

The application of surface forces that may be associated with the

techniques used to develop a desired surface topography can, in the
absence of sufficient energy to produce recrystallization, result in a
lattice distortion, such as that indicated in Fig. 7. The application o f
a force normal to the su rface, that i s , a compressive fo rc e , causes
forces X 2 and X 3 to develop. The resultant force normal to the sur­
face , X 3 , will cause distortion in the crystal lattice.

IV. CHEMISTRY OF SURFACES

Clean surfaces of solids are extremely chemically a ctive. The surface
atoms of an elemental metal, for example, are highly en ergetic. They
are bound by like atoms everywhere but at the free surface. This
boundary is depicted schematically in Fig. 8 . A copper atom, for e x ­
ample , which lies in a ( 1 1 1 ) plane in the bulk o f the solid will have a
coordination number of 1 2 , that i s , it is bonded to 1 2 nearest neigh­
bors. That same copper atom at the su rface, how ever, will have a co­
ordination number of only 9. It has only nine nearest neighbors,
three less than when it is in the bulk solid. T h u s, the energy that
normally would be associated with bonding to three additional like
atoms is now available at the surface. This en ergy, expressed over
an area consisting of many atoms in the surface lattice, is referred to
as the surface energy.
Another way of looking at surface energy is to understand it as
being the energy necessary to generate a new solid surface. This can
be accomplished by the separation of adjacent planes in the solid. The
energy required for separation is a function of atomic packing. For
example, in copper the atomic packing density is greatest in ( 1 1 1 )
planes (greatest number of nearest neighbors within the plane). As a
22 Buckley

Surface

F ig . 8. Surface atoms (schem atic). Since these atoms are not entirely
surrounded by others, they possess more energy than internal atoms.

result the bonding force between adjacent ( 1 1 1 ) planes is least and,

therefore, the surface energy of new ( 1 1 1 ) surfaces generated, say by
cleavage, is less than it is for other planes, such as the ( 1 1 0 ) and
(100) planes. This lesser binding strength is also reflected in the
distance between adjacent planes—it being greater between adjacent
( 1 1 1 ) planes than between other planes, such as the ( 1 1 0 ) and ( 1 0 0 )
planes.
Because the atoms at the surface have this unused en ergy, they
can interact with each o th er, with other atoms from the bu lk, and with
species from the environment. One of the things these surface atoms
can d o , because they are not bound as rigidly as atoms in the bu lk, is
alter their lattice spacing at the surface (F ig . 9). This process is

• SOLUTE
O SOLVENT

oooooo
OOOOOO
RECONSTRUCTION SEGREGATION
(a) (b)

Fig. 9. Possible chemical surface even ts. (a ) Reconstruction; (b )

segregation.
Surfaces 23

commonly called reconstruction. Low-energy electron diffraction

(LEED) studies have revealed reconstructed surfaces in some crystal­
line solids, but not in oth ers.
Another event that can occur in solids containing more than a sin­
gle element (e . g . , alloys) is the diffusion to and segregation at the
surface o f atoms from the bu lk. In a simple binary a lloy, for example,
the solute atoms can diffuse from the near-surface regions to the su r­
face and completely cover the surface o f the solvent. This has been
observed for many binary alloy systems including aluminum in cop p er,
tin in copper, indium in copper, aluminum in iron, and silicon in iron.
The process of surface segregation is depicted schematically in Fig. 9.
The segregation mechanism is not really understood. One h y ­
pothesis is that the solute segregates on the surface because segrega­
tion reduces the surface en ergy. A second theory is that the solute
produces a strain in the crystal lattice of the solven t, and th a t, be­
cause of this unnatural lattice state, there is a necessary driving
force to eject the solute atoms from the bulk. The result of this is
segregation at the surface.
With ionic crystalline solids, surface charging can occur due to
unequal vacancy en ergies. Near-surface vacancies in these solids may
be either positively or negatively charged. The energy associated
with the formation of these vacancies v a rie s , and an excess of one or
the other type of vacancy occurs. This excess causes a voltage be­
tween the surface and the interior of the solid. The overall energy
of the system is decreased when there is an excess of positively
charged ion vacancies in the solid, and these migrate toward the sur­
face. When in the bulk (F ig . 10a) , they will bring about an internal
arrangement of vacancy charges (F ig . 1 0 b) such that the positive
charge exists near the su rface, and the Debye charged layer will form.
This layer will have no effect on the behavior of the solid su rface, as
in , for example, its interaction with an adhesive.
A great deal of concern must be given to the surface of polymers
just as to the surfaces of metals and ionic solids. There are a host of
variables in the preparation process that can alter the chemistry of a
polymer su rface, just as the mode of preparation can, for example, al­
ter the topography of a metal surface. With polym ers, not only is the
physical mode of surface preparation important, but also the environ­
ment in which the surface is prepared can pronouncedly affect poly­
mer surface chemistry.
The effect o f the environment in which polymers are prepared
has been carefully studied with electron spectroscopy for chemical
analysis (E S C A ). Electron spectroscopy for chemical analysis, or x-
ray photoemission spectroscopy (X P S) as it is currently called, p er­
mits analysis of surfaces by measuring both the energies associated
with electron levels in atoms and molecules and shifts in electron ener-
24 Buckley

0 0 0 0 © ® ®
□ EJ 0 □ □

□ 0 □
0
0
□
(b)

Fig. 10. Formation of Debye layers in ionic crystals due to unequal

vacancy-formation energies where E~E+ . Positive-ion vacancies are
represented by - because o f their effective negative ch arge, and nega­
tive ion vacancies by +. (a ) Uniform distribution of positive-ion and
negative-ion vacancies, which are present in different amounts b e ­
cause of different energies of vacancy formation. A voltage is formed
between the surface and the interior of the crystal, (b ) The overall
energy of the crystal is decreased when the excess positive-ion va ­
cancies migrate toward the su rface, forming a Debye space-charge
layer. The interior o f the crystal below the Debye layer now possess­
es equal numbers of positive-ion vacancies and negative-ion vacancies.

gies accompanying various chemical reactions. It is a surface-sensi­

tive tool.
Films of high-density polyethylene were prepared from powders
by hand-pressing the powder between sheets of clean aluminum foil at
200°C, the minimum temperature needed to ensure plastic flow . Sam­
ples from identical powders were prepared in three different environ­
ments: in a ir , in n itrogen , and, after being pumped down to 1 0 " 14
T o r r , in pure nitrogen or argon. The surfaces were examined with
XPS for both oxygen (0 ^ s) and carbon ( C i s ) .
The OjLS and C^s spectra corresponding to samples from the three
modes of preparation are markedly different (F ig . l l a - c ) . ( A T R ) and
(T IR ) experiments did not reveal the presence of any oxygen functions
(-O H , / C = 0 , C - O - C , e tc . ) , and, in fa c t, the spectra were v ir ­
tually identical. This demonstrates the great power o f XPS to d is­
tinguish minute differences in samples when such differences are local­
ized at or near the surface. Comparison with the data for low-density
polyethylene and with model monomer systems shows that the 0 ^g sig ­
nal arises from )>C= 0 environments. The three methods o f prepar-
Surfaces

1s

(b)

(a)

537 535 533 531 289 287 285 283

Binding energy, eV

Fig. 11. X-ray photoemission spectroscopy analysis of C^g and 0^s

levels of high-density polyethylene films pressed (a ) in air; (b ) in
nitrogen; (c ) after gasification in a 10" 14 T o rr vacuum, in pure ni­
trogen or argon.
26 Buckley

ation clearly indicate that "unoxidized" surfaces may most readily be

prepared by excluding all traces of oxygen during the pressing sta ge.
On leaving samples exposed to the atmosphere for some time, hydrogen
from extraneous water in the atmosphere bonds to the surface /C= 0
groups, and the 0 ^s peak then acquires the characteristic doublet na­
ture. A ga in , ATR and TIR do not reveal any changes since the hy­
drogen bonding is localized at the surface [4] .

A. Chem isorption

In addition to the characteristics the solid surface itself displays, the

surface can interact with the environment. This interaction is e x ­
tremely important because it alters the surface chem istry, ph ysics,
m etallurgy, and mechanical behavior. I f a metal surface is ve ry care­
fully cleaned in a vacuum system, and then a gas such as oxygen is
admitted to the system, the gas will adsorb on the metal surface. This
interaction results in strong bonds being formed between the metal
and the adsorbing species. With the exception o f inert gases, this ad­
sorption results in bonding which is chemical in nature. The process
is referred to as chemisorption. It is indicated schematically in Fig.
12. Once adsorbed, these films are generally difficult to remove.
Where the species adsorbing on a clean surface is elemental, the
adsorption is d ire ct. The atoms in the surface of the solid retain their
individual identity, as do the atoms of the adsorbate; yet each is
chemically bonded to the other. When the adsorbing species is molec­
ular , chemisorption may be a two-step process — dissociation of the
molecule on contact with the en ergetic, clean surface followed by ad­
sorption of the dissociated constituents.
Chemisorption is a monolayer process. Furthermore, the bond
strengths that exist between the adsorbing species and the solid sur­
face are a function of chemical activity of the solid surface (surface
e n e r g y ), the degree of surface coverage o f that adsorbate or another
adsorbate, the reactivity of the adsorbing species, and its structu re.
The surface energy of the solid surface is important because the
more energetic the surface, the stronger is the tendency to chemisorb.
The effect of surface energy can be demonstrated by examining va ri­
ous crystallographie planes of a single metal. In general, the high-
en ergy, low —atomic - density planes will chemisorb environmental spe­
cies much more rapidly than will the high-density, low -surface-energy
planes. This has been demonstrated experimentally to be the case.
Hydrogen sulfide will adsorb more readily on (110) and (100) surfaces
of copper than on ( 1 1 1 ) surfaces.
When different solid surface materials are considered, adsorption
differences are also observed. For example, copper, silver, and gold
are the noble metals, and many of their properties are considered
v e ry similar. Yet with respect to chemisorption of a gas, such as
Surfaces 27

f | ADSORBATE
O SOLID

o% o% o% o l o U
OOOOOO OOOOOO
oooooo oooooo
CHEMISORPTION COMPOUND
FO RM A TIO N

F ig . 12. Chemisorption and compound formation on solid surfaces.

oxygen, considerable differences are observed. Oxygen will chemi-

sorb relatively strongly on copper, weakly on s ilv e r , and not at all on
gold.
The reactivity o f the adsorbing species is also ve ry important.
Examination of the halogen family indicates that fluorine will adsorb
more strongly than chlorine, chlorine more strongly than bromine, and
bromine more strongly than iodine.
The structure of the adsorbing species is also ve ry significant in
surface bonding and chemisorption. This can be demonstrated with
the adsorption of simple hydrocarbons. Something as simple as the
degree of bond saturation in the molecule will make a difference. I f
ethane, ethylene, and acetylene are adsorbed on an iron surface, the
tenacity of the resulting chemisorbed films is in direct relation to the
degree of bond unsaturation. Acetylene is much more strongly bound
to the surface than ethylene i s , which, in tu rn , is more strongly
bound than ethane i s . The simple explanation for this is that the un-
saturated carbon-to-carbon bonds break on adsorption and bond to
the iron. The greater the number of carbon-to-carbon bonds, the
greater the number of potential bonds from the hydrocarbon molecule
to iron.

B. Compound Formation

Compound formation on the surface of solids is extremely important.

The naturally occurring oxides present on metal surfaces prevent
their destruction when in contact with other solids. Furthermore,
their presence can alter deformation behavior. Solids and liquids can
readily react with clean solid surfaces to form compounds whose p res­
ence can alter surface properties.
Chemisorbed films can often interact with a surface to form chem­
ical compounds. When this occurs, the surface material and the ad-
sorbate lose their individual identities and form an entirely new sub­
28 Buckley

stance with its own prop erties. Unlike chemisorption, which is simply
a monolayer process, constituents from the environment can react with
the solid surface by diffusion of the solid surface material into the
compound and diffusion of the environmental species into the film .
The compound can continue to thicken on the surface i f the film is po­
rous and allows for the two-way diffusion to occur (Fig1. 1 2 ).
An example of the formation of a porous compound on a surface is
the ru s t, or iron o xid e, produced in the oxidation of iron in a moist
air environment. The oxidation process will continue to consume the
iro n . In contrast, the oxidation of aluminum to form aluminum oxide
results in the formation of a th in , dense oxide which, because of the
film?s d en sity, retards diffusion and further growth.

Co M etallurgical Effects

Surface behavior is altered by the presence of grain boundaries on the

surface of crystalline solids as well as by other surface d efects. For
example, grain boundaries, in addition to having a chemical effect
because of their high e n e rg y , also influence mechanical prop erties.
The microhardness is generally higher in grain boundaries than it is
in grains [ 5] . This hardness effect is seen in the data for iron in
Fig. 13 which shows th a t, as the grain boundary is approached, the
hardness increases. The hardness is at a maximum directly in the
boundary. The increase is marked and not marginal.
The increase in hardness seen in the grain boundary of Fig. 13
can be explained on the basis of what has already been discussed re l­
ative to grain boundaries. They are regions o f high dislocation con­
centration and lattice strain. Strained metal has a higher dislocation
concentration than the annealed or strain-free material, and the con­
centration generally will increase with increased deformation until re-
crystallization occurs.
Dislocations, like grain boundaries, are higher energy sites on a
surface than nondislocation areas. It is for this reason that strained
metal surfaces are chemically more active than annealed or strain-free
surfaces a re . This chemical activity of dislocation sites can be de­
monstrated by a technique called etch pitting. Certain chemical
agents will react on the surface of a material, and, because of the
more energetic nature (i.e . , greater reaction rates) of the disloca­
tions , these sites will be preferentially etched. The result is that pits
are left on the surface at each dislocation site. From these pits it is
possible to identify the location and concentration of the dislocations.
The literature lists the necessary reagents required for etch pitting
various materials.
Surfaces 29

DISTANCE FROM GR A IN BOUNDARY,,um

F ig . 13. Microhardness traverse across a grain boundary in iron con­

taining 0. 02% oxygen. (From R ef. 5.)

V. SURFACE FILM EFFECTS

The properties of solid surfaces are markedly altered by the presence

of foreign substances. An atomically clean metal surface has certain
characteristic chemical, physical, and metallurgical prop erties. Just
as soon as something interacts chemically with that surface, those
properties are changed. This fact is extremely important to under­
stand because most real surfaces are found, not in the atomically clean
state, but rather with film (s) present on their su rface, as has already
been discussed in reference to Fig. 1.
It can safely be said that the wide variations found in the litera­
ture for the surface properties of materials can be directly attributed
to the effect of these film s. Some surfaces are more strongly influen­
ced by these films than oth ers, and the specific film composition will
produce varying effects.
30 Buckley

The presence of oxides on metal surfaces has been observed to

produce surface hardening. Roscoe, in some v e ry fine experiments
conducted in the 1930s, demonstrated this effect with cadmium oxide
present on a cadmium surface [ 6 ] . Since that time it has been demon­
strated by other investigators who observed dislocations emerging at
the surface with the oxide impeding their mobility.
While oxides and some other films produce surface hardening,
other surface films increase du ctility. For example, water on alkali
halide crystals allows an otherwise brittle solid to deform plastically.
Water has the same effect on ceramics.
Magnesium oxide (MgO) is normally a ve ry brittle material with a
Knoop surface hardness in the clean state of about 750 kg/mm^. When
MgO is cleaved under a hydrocarbon such as toluene so as to exclude
moisture, a hardness value of this magnitude is measured for the MgO
surface. If, how ever, the MgO is cleaved in moist air where the
freshly generated clean surface can interact with the moisture in the
a ir , a different result is obtained (F ig . 14).
Figure 14 presents the hardness of MgO as a function of indenta­
tion time in two environments, dry toluene and moist air. The in ­
creased surface ductility in the presence of water is striking. Not
only is there an appreciable difference in hardness, but also that d if­
ference increases with increasing indentation time. The hardness in
moist air decreases with increasing indentation time; in dry toluene,
the hardness is unchanged. It is this change with time that makes
the film effect a true surface property and not simply a lubricating
effect produced by the water.

INDENTATION TIME IN SECONDS

F ig . 14. Illustration of the time dependence of microhardness o f MgO

in moist air. (From Ref. 7.)
Surfaces 31

In the late 1920s, the Russian researchers V. I . Likhtman et al.

found that the presence of certain organic molecules on the surface o f
solids produced a softening effect [ 8 ]. Mechanical behavior was alter­
ed by these films. Such substances as oleic acid in Vaseline oil are
examples of materials examined. This effect is important because many
of the materials studied are commonly found substances. The surface
softening can be v e ry beneficial in certain instances, such as in the
arrest of the formation of fatigue cracks.

V I. C H A R A C T E R IZ A T IO N OF SURFACES

A. Microscopy

The nature and character of the surface is extremely important to the

understanding of the performance of that surface in adhesive systems.
Microscopy has been , and probably still i s , the most common technique
employed for the characterization of surfaces. The magnification of
surfaces to identify structure dates back at least to the sixteenth cen­
tury. With simple lenses the features o f surfaces could be magnified
1 0 0 times.
The optical microscope was developed in the 1700s, and its avail­
ability really initiated the effective characterization of surfaces. It
became the most effective tool for the study o f surfaces, and it r e ­
mains that to this day. With the aid of oil immersion, the ordinary
optical microscope can yield detailed surface features at magnifications
ranging to about 500—1000. Thus, the character and structure of
grain boundaries in metals and alloys are readily identifiable.
The development of the electron microscope was a notable advance
because it permitted magnifications from 10 to 100,000. For the first
time, atomistic features of surfaces were identifiable, and rows of
atoms on the surface could be readily seen. Today, electron micro­
scopy is used routinely to identify and characterize dislocation struc­
tures in materials.
In the 1950s, with the development of the field ion microscope by
Mueller and Tsong [ 9] , it became possible to characterize surface
structure at the level of the individual atom. At this point in the de­
velopment of research instrumentation it must be said that, for struc­
tural analysis, the field ion microscope is the ultimate tool because it
identifies individual atom sites on a solid surface. Thus, each in d ivi­
dual white spot in the field ion micrograph of Fig. 15 represents an in ­
dividual atom site while the rings represent atomic planes.
The field ion microscope has been adapted for use in adhesive
studies and in the characterization of surfaces in such studies. F ig­
ure 15 is a photomicrograph of a tungsten surface. The micrograph
reveals the atoms and planes. The ring just to the upper right of
center is the (110) plane of tungsten. Each row out from the center
32 Buckley

F ig . 15. Field ion micrograph of a tungsten surface (16.0 kV) prior

to contact.

ring represents the layer of atoms next nearest to the surface. The
field ion microscope is so sensitive that it can be used to detect the
absence of a single atom from the surface or, con versely, the presence
of an extra or a foreign atom.
In recent years the atom probe has been developed for the deter­
mination of single-atom chemistry. When used in conjunction with the
field ion microscope, the atom probe can not only characterize the
structural arrangement of individual atoms in a solid su rface, but also
determine the chemistry of an individual atom present in the surface.

B. Etching

Etching is the interaction of surfaces with chemical agents such as

acids or bases. In simple metals in the polycrystalline form , the crys-
tallographic orientation of each adjacent grain at the surface will vary.
Surfaces 33

The energy of these surfaces will v a r y , and they w ill, therefore, react
at differin g rates with a particular chemical agen t. T h u s, in a crude
way, one can distinguish the more atomically dense surface planes
from the less dense. The more dense planes have lower surface en er­
gies and, th erefore, will not be as readily attacked as the less dense
planes.
Etching can b e , and has b een , v e ry effectively used as a techni­
que for revealing grain boundaries in metals. Grain boundaries are
sites o f higher energy than the surfaces of the individual grains and,
th erefore, they will be preferentially attacked. Furthermore, d iffe r ­
ent phases in alloys will etch differently at the surface. The chemical
reagents for such etching are available in standard metallurgical hand­
books .
In addition to identifying orientation, grain boundaries, and
phases, etchants can be used to identify atomistic defects such as d is­
locations , the atomic line defects in crystalline materials referred to
earlier. The proper etchant can not only indicate the concentration of
dislocations at the su rface, but also reveal their locations. Further­
more , etchants reveal the atomic plane upon which a dislocation lie s .
A wealth of useful information can be acquired about a surface
by the use of the optical microscope and etching techniques. The use
o f simple, chemical spot tests in conjunction with the foregoing can
provide insight into the chemistry of the solid surface. These tests
require the use o f readily available chemical reagents which, when ap­
plied to the su rface, will reveal the metallic element present in the
su rface. Many standard college chemistry textbooks on inorganic
qualitative analysis list the required materials.
The chemical spot test can be used to detect adhesive transfer to
surfaces where dissimilar materials are in contact. A permanent pat­
tern of an element’s distribution on a surface can be obtained i f a
porous p a p er, such as filter pap er, is impregnated with the chemical
rea gen ts. The paper is pressed against the surface to be analyzed;
then the paper is moistened. A map of the location of the elements
thus appears on the paper.

C. A nalytical S urface Tools

The field ion microscope and the atom probe have already been dis­
cussed . These tools have been used in adhesive studies to character­
ize surfaces before and after adhesive contacts.
A host o f analytical tools has been developed in recent years to
characterize the real nature o f solid surfaces. Some operate on the
principle of atomic arrangement in the surface layers of crystalline
solids. One such device is LEED. This surface tool can be very use­
ful to those interested in surfaces. It analyzes, by an electron dif-
34 Buckley

fraction technique, the general atomic arrangement of the outermost

surface layers of a solid. A rudimentary understanding o f atomic
arrangement will assist in understanding the nature of the surface
structure.
With the exception of amorphous carbon, glasses, and some
polymers , nearly all materials—including metals, alloys, ceramics ,
solid lubricants, and graphitic carbon are crystallin e. This means
that the atoms or molecules are arranged in accordance with particu­
lar structures that can readily be id en tified. These structures are
mostly cubic and hexagonal. The cubic structure can be further sub­
divided into the face-centered cubic structure and the body-centered
cubic structures.
Metals such as copper, nickel, s ilv e r , gold , platinum, and alu­
minum have a face-centered cubic structure, while metals such as
iro n , tantalum, niobium, vanadium, and tungsten have a body-center­
ed cubic structure. A number of metals—including zinc , cadmium, co­
balt , rhenium, zirconium, and titanium—have a hexagonal crystal
structure.
The atoms making up the faces of the cube for the face-centered
cubic and the body-centered cubic are referred to as the ( 1 0 0 ) sur­
faces. They constitute planes of atoms that can move relative to each
other when the crystal is deformed plastically and are, th erefo re, also
referred to as slip planes within the crystal. Under applied stresses
these [the ( 1 0 0 ) ] planes are one o f the sets o f planes most commonly
observed to slip over one another in the body-centered cubic system.
A third set of planes in the cubic system are the (111) planes.
They are the planes on which slip and cleavage in face-centered cubic
materials are most frequently observed to occur. There are other
planes that may be observed as well. For example, i f one were to use
x-ra y diffraction , electron channeling, or some other technique for
the determination of crystaliographie orientations , a host of different
crystalio graphic planes would appear in each grain of a polycrystalline
sample analyzed.
The (111) planes in the face-centered cubic crystal are the
planes o f closest atomic packing, as already mentioned. The atoms
occupy the least area for the number of planes involved. When a
( 1 1 1 ) plane is present on a surface, it has the lowest surface energy
in the face-centered cubic system and, therefore, is the least likely
to interact chemically with environmental constituents.
The (110) planes in the face-centered cubic system are the least
densely packed. The two outer rows of atoms as well as the center
row are outermost with the two in-between rows below these. The
( 1 1 0 ) planes have higher surface energies than the ( 1 1 1 ) planes and
are, therefore, much more reactive. Furthermore, because they are
less densely packed, their mechanical behavior, such as elastic modu­
lus and microhardness, is also less than is observed for the ( 1 1 1 )
planes.
Surfaces 35

On any particular crystallographic plane present on the surface,

the atomic packing can vary with direction of movement. For example,
on a (111) surface, two basic directional packing variations exist.
Surface energies also vary with these two directions.

1. L o w -en erg y electron d iffra c tio n (LE ED )

Low-energy electron diffraction is a very widely used surface tool for
characterization of the surface atomic structure seen on crystalline
solids. Because the device detects the surface crystal structure,
single crystals are generally studied although large-grained poly­
crystals can also be examined. Low -energy electrons in the range of

(c)

F ig . 16. Low-energy electron diffraction patterns of iron (O i l) su r­

face (110 V ). (a ) Carbon contaminants; (b ) argon bombarded; (c )
clean surface.
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Title: Kaffe ja Tupakki

Author: Gustaf Erik Eurén

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Language: Finnish

Credits: Produced by Tapio Riikonen

*** START OF THE PROJECT GUTENBERG EBOOK KAFFE JA

TUPAKKI ***
Produced by Tapio Riikonen

KAFFE JA TUPAKKI
Kirj.

Gustaf Erik Eurén

Lukemisia kansalle. N:o 46.

Turussa, J. W. Lilja & Co:n kirjapainossa, 1855.

Imprimatur: C. A. Sanmark.
 Kaffepuu.

Niinkuin ihmisten elämässä yksi kansa on toista merkillisempi ja

usein yksi ihminen kansan seassa merkillisempi kuin koko kansa
yhteensä, niin on kasvaimienki seassa toinen kasvulai toistansa
merkillisempi ja monasti on yksi ainoa kasvain kaikkein
heimolaistensa joukossa ylimäärin tunnettu ja ihmeellinen.
Leipäkasvut ovat kaikkina maailman aikoina arvattavasti olleet
merkillisimmät, ja niitä lähimmät ovat muut ihmisten syötävät
kasvaimet. Sitten tulevat ihmisten vaatteiksi kelpaavaiset kasvaimet.
Lopuksi ovat eläinten syötävät kasvaimet saaneet suuremman arvon.
Muista tietävät tuskin muut kuin oppineet mitään. Kaikkein
kasvaimien seassa, jotka ihmisten nautinnoksi ovat käytetyt, on
kaffepuu saanut suuren merkillisyyden. Kaikkein nautittavain
kasvujen seassa on se saanut yhtä suuren merkillisyyden kuin
puuvilla (pumpuli) verhokasvujen seassa.

Arabiassa ja Javan luodolla nousee kaffepuu 8-10 kyynärän

korkuiseksi, mutta länsi-Indiassa ei sitä päästetä siihen korkeuteen,
vaan leikataan oksat poikki ajallansa, josta se paremmin vesoo, tulee
haaraisemmaksi ja antaa niin enemmän hedelmiä. Oksat ovat toinen
toistansa vastaiset, lehdet samaten, jotka aina viheriöitsevät.
Valkoiset ja hyvähajuiset kukkaset istuvat rypälettäin lehtien
loukossa. Kukoistaissansa näyttää kaffepuu ikäänkuin lumelta
peitettynä, enemmänki kuin meidän omenapuumme, jotka myös
kyllä kukassa ollessansa lumittuneelta näyttävät. Kukkasia seuraa
punainen hedelmä, joka sekä muotonsa että kokonsa vuoksi on
kirsipuun marjan kaltainen, suurempi ja punaisempi kuin tuomen
marja. Sen marjan mehussa on kaksi siementä, joiden toinen puoli
on tasainen, toinen ympyrämäinen. Nämät kutsutaan kaffepöönäksi
(kaffeherneeksi), joka on väärä nimi koska ei hedelmä ole palko
vaan marja. Jo toisena vuonna kantaa kaffepuu hedelmiä, mutta
täysisatoinen on se vasta neljäntenä eli viidentenä vuonna. Se vaatii
lämpimiä maita, ehkä ei se salli kovaa kuumuutta. Kuumissa maan
paikoissa istutetaan se muiden puiden varjoon ja kaipaa aina
märkyyttä.

Arabian saarento on enimmiten santamaata, kovin lämmin ja

melkein sateeton; mutta sen eteläisessä päässä, jonkun matkan
meren rannasta, on vähän kalpeampi ilma, vuorinen maakunta ja
tarpeellinen paljous sadetta. Täällä onnellisessa Arabiassa (niinkuin
sitä osaa on kutsuttu; sen oma nimi on Yemen) luultiin kauan aikaa
kaffepuun kotomaan olevan. Mutta nyt tiedetään että kaffepuu
Egyptin maasta eteläänpäin, Abyssiniassa ja vieläkin eteläisemmissä
maissa, Enarea ja Kaffa, kasvaa villipuuna metsissä. Tästä päättäen
on kaffepuu Arabiassa istutettu, tuotuansa sinne nimitetyistä Afrikan
maakunnista.

Useimpain ja merkillisimpäin asiain alku on aina ollut satuisessa

hämärässä. Tosien asiain siaan kerrotaan satuisia juttuja. Niin on
puhe kaffeherneenki ensimäisestä nautitsemisesta melkein turhaa
tarinata, joka kerrotaan seuraavalla tavalla: Eräs mahometilaisen
luostarin esimies oli havainnut kuinka kutut, tätä hedelmätä
nautittuansa, tulivat valppaiksi, juokseskentelivat ja hyppelivät
yökaudet. Tämä saatti hänen valmistamaan tästä hedelmästä
juomaa, joka pitäisi sekä hänen että luostarin muut kirkonpalveliat
valppaina, koska heidän koko yön täytyi templissä rukouksia pitää.

Kaffejuominen kuuluu kokonaan kykyisempiin aikoihin. Vanhat

Grekalaiset ja Romalaiset eivät tästä juomasta tienneet mitään. Eräs
vanha arabialainen kirja asettaa kaffejuomisen 15 vuosisadan
keskipaikoille, josta päättäen se olisi noin 400 vuoden vanha. Tämä
arabialainen kirjoitus kertoo kaffejuoman syntymisen seuraavalla
tavalla: Arabian eteläisellä rantamaalla, Adenissa, oli eräs mufti (iso-
pappi), nimeltä Gemaledin. Punaisen meren länsirannoilla
matkustaissansa kohtasi hän muutamia kansalaisiansa, jotka
nautitsivat kaffejuomaa. Kotiin tultuansa arveli hän tämän juoman
terveelliseksi ja havaitsikin koettuansa sen tekevän pään selkeäksi ja
vastustelevan unta, jonka tähden hän säätti sitä juomaa kirkon
palvelioille, jotka yörukouksia pitivät. Mutta nämät katsoivat sen
päivälläkin nautittuna hyväksi. Näistä levisi kaffejuoman
nautitseminen, ensin Adenissa sitten koko Arabiassa ja myös Mekka
nimisessä kaupungissa, josta se, koska kukin mahometilainen on
vaadittu sinne kerran elämässänsä vaeltamaan, pian levisi kaikkein
mahometilaisten maihin. Tässä tosin ei ole kaffejuomisen alkua
osoitettu, mutta kuitenki sen leviäminen Arabiassa, josta se sitten yli
koko maailman on saatettu.

Vuonna 1511 lähetti Egyptin Ruhtinas uuden maaherran Mekkaan.

Tämä, joka ei tätä juomaa tuntenut, suuttui kovasti nähdessänsä
kerran kaupungin suuressa kirkossa kirkonpalveliain istuvan loukossa
ja juovan kaffejuomaa. Hän ajoi nämät ulos kirkosta ja kutsui kokoon
jumalisia, lainoppineita ja muita kaupungin ymmärtäviä miehiä, jotka
kauan tästä asiasta tuumailivat. Yksi niistä sanoi toisten pilaksi että
kaffe niinkuin viinakin saattaa juovuksiin, jonka hän tiesi siitä että
hän oli kaffeeta maistanut. Mutta koska laki kielsi kaikkia semmoisia
väkeviä juomia maistamasta, sai hän rikoksestansa laissa määrätyn
raipparangaistuksen. Koska nämät kokoontuneet eivät taitaneet tulla
mihinkään päätökseen, kysyttiin lääkäreitä. Maaherra kutsui kaksi
lääkäriä, jotka sanoivat kaffejuoman terveydelle vahingolliseksi,
jonka tähden se juoma kirottiin. Sitä kiellettiin myymästä, kaikki
aseet ja astiat poltettiin ja se, joka sitä joi, kuljetettiin aasin selässä
pilkaksi ympäri kaupunkia. Mutta tämä kielto ei ollut pitkällinen, sillä
ruhtinas itse Kairossa oli hyvä kaffejuomari ja hänen oppineimmat
miehensä todistivat sen vahingoitsemattomaksi ja luvalliseksi. Tämän
voiton perästä tuli kaffe vieläkin suurempaan huutoon ja tietoon.

Parin kymmenen vuoden kuluttua sattui kuitenki Kairossa (Egyptin

pääkaupungissa) jonkun kiihkomielisen päähän ruveta saarnaamaan
oikeata sotaa kaffejuomaa vastaan, joka nyt oli tuttu jokaisessa
pienimmässäkin kaupungin töllissä. Hän saarnasi sanoen ettei
yksikään kaffejuomari ole oikia mahometilainen. Häneen mieltyneet
oikiauskoiset ihmiset tulivat tästä niin villiin, että he kirkosta
tultuansa ryntäsivät kaffehuoneisiin sisälle, löivät palasiksi kupit ja
pöydät sekä pahasti tupuloitsivat kaikki juomarit. Koko kaupunki
jakausi kahteen viholliseen lahkoon, kaffejuomarien ja kaffesotiain.
Kapina ja meteli oli hirmuinen. Kaupungin ylimmäinen tuomari kutsui
oppineita kokoon ja nämät väittivät yksimielisesti että jo aikoja sitten
oli tietty asia että kaffejuoma olisi sekä luvallinen että hyödyllinen.
Kokouksen esimies tarjosi päälliseksi kaikille kaffeeta ja otti itse
ensimäisen kupin. Tämä uusi voitto levitti vieläkin enemmin kaffeen
sekä huudon että nauttimisen. Niin tekevät ainakin ajattelemattomat
vähämieliset ihmiset, turhasta ottavat suuren äänen ja tekevät sen,
mitä he parantaa aikovat, kahta pahemmaksi.

Vuonna 1554 asetti kaksi miestä erinäisen kaffehuoneen

Konstantinopolissa; siellä oli hienot istuimet, tarittiin kaffeeta, juotiin,
pelattiin schack-peliä ja iloittiin. Eräs turkkilainen runoseppä laati
runon kaffeen kunniaksi. Kaffehuonetten luku kasvoi kasvamistansa
niin että papit rupesivat valittamaan kaffehuoneissa käytävän
enemmin kuin kirkoissa. Mufti selitti että kaffejuominen on kielty
koranissa (mahometilaisten bibliassa), josta syystä kaikki
kaffehuoneet suljettiin. Mutta uusi Mufti rakasti kaffeeta, häntä
seurasi muu papisto ja hovi ja koko kaupunki. Sittemmin on kyllä
välistäin täällä kaffehuoneet tulleet suljetuksi, mutta ei itse
kaffejuoman tähden, vaan valtakunnallisista syistä, koska kansalla oli
näissä hyvä tilaisuus pakinoita hallituksen asioista. Kaffeen juominen
on siitä asti levinnyt leviämistänsä. Suuremmissa taloissa otettiin
erityinen palvelia kaffejuomaa valmistamaan ja taritsemaan. Vihdoin
tehtiin laki, joka määräsi vaimolla olevan syyn avioliitostansa päästä,
jos hänen miehensä kielsi hänen kaffeeta juomasta.

Näin tuli Itämaalla kaffejuominen tavaksi 17 vuosisadalla eli 150

vuotta sen ensimäisestä alkamisesta Arabiassa. Tähän asti tunnettiin
sitä tuskin nimeksikään muualla Europassa. Luultavasti tuli se ensin
Venedigin suureen kauppakaupunkiin, sillä eräs Pietro della Valle
kirjoittaa vuonna 1615 Konstantinopolista tahtovansa ottaa Italiaan
palatessansa vähän kaffeeta myötänsä. Vuonna 1660 toivat
muutamat Turkin maalta palaavaiset kauppamiehet kaffeherneitä
myötänsä Marseljiin ja näyttelivät sekä niitä että muita siihen
kuuluvia aseita ja astioita niinkuin joitakin kummallisia kappaleita;
mutta jo vuonna 1671 avattiin siellä ensimäinen kaffehuone. Eräs
englantilainen kauppamies, Edwards, otti Smyrnasta palatessansa
grekalaisen neidon myötänsä kaffeeta hänelle valmistamaan. Tämä
neito nai erään ajajan (kuskin), joka parikunta avasi ensimäisen
kaffehuoneen Londoossa. Parisissa avattiin samoin ensimäinen
kaffehuone 1672, koska Turkin Sultanin Mahomed IV:nen
lähettiläinen siellä oli pitemmän ajan oleskellut ja hovillekin tätä
uutta juomaa tarjonnut. Marseljissa nousi kuitenki vielä pieni riita
kaffen juomisesta. Lääkärit katsoivat sen vahingolliseksi ja saattivat
sen julkisen keskustelemisen alle. Kutsumuskirjassa, joka vielä on
tallella, käskivät lääkärit tulemaan raadihuoneesen taistelemaan
asiasta, mutta se vaikutti saman kuin mahometilaistenki vihollisuus,
ehkä ei kaffejuoman puolustajillakaan aina ollut peräti vakavia ja
luotettavia perustuksia, sillä äsken nimitetty kutsumuskirja sotii
semmoisia perustuksia vastaan, joilla puolustajat olivat tahtoneet
kaffejuoman hyväksi näyttää, niinkuin että se turkin kielellä
nimitetään bon (joka franskan kielellä merkitsee: hyvä) ja että se on
kotoisin onnellisesta Arabiasta.

Jälemmin tuli kaffe tutuksi pohjaisissa maakunnissa. Vuonna 1665

ei sitä vielä tunnettu Danskan maallakaan. Onpa sillä ollut täälläkin
vastustajansa; viimis vuosisadan lopulla kiellettiin kaffejuominen
sekä Ruotsissa että Suomessa. Mutta ei se siitä lakannut. Kaffeeta
keitettiin riihissä ja metsissä; ja koska kaffeella keittäissä on oma
helposti tunnettava hajunsa, poltettiin katajan hakoja niin
sekoitettaaksensa kaffen hajun. Niin paljo oli jo kaffejuominen
vallassa ettei kielto taitanut sitä enään takaisin tunkea, jonka tähden
kielto viimein peräytettiinki. Siitä asti on kaffe levinnyt Suomessakin
että tuskin enää löytyy maassamme sitä tölliäkään, jossa ei se olisi
tunnettu.

Onhan toki kaffeella vieläkin vastusteliansa, vaikka kyllä turhaan

sitä vastustellaan. Sitä juodaan koko maassa, ehkä muutamat
arkamieliset kynsivät päätänsä sanoen sen joko vahingolliseksi
juomareille taikka vahingolliseksi maalle, koska se on ulkomailta
ostettava.

Mitä ensin sen vahingollisuuteen juojille tulee, niin on siitä kaikkina

aikoina viisasteltu niinkuin jo edellä olemme kertoneet. Alkehisto,
joka kaikkein kappalten alkuaineet tutkii, näyttää että kaffeherneessä
on enempi häkkyainetta kuin missäkään muussa tunnetussa
kasvaimessa, ja häkkyaine on lihan pääaine. Siis on kaffeherne ja
kaffejuominen suureksi palkinnoksi niille, jotka aivan vähän lihaa
saavat syödäksensä. Tästä taidamme selittää miksi ihmisille on niin
suuri halu tämän juoman perään; syy on se että se on paljo
ravitseva. Ulkomaan valtakunnissa, joissa kaikista ihmisen elämään
kuuluvista asioista tarkka vaari otetaan, on havaittu että lihan
syöminen samassa mitassa on vähennyt kuin kaffeen nauttiminen on
enennyt. Tässä on toinen todistus siitä että kaffeherneessä on
samaa ainetta kuin lihassakin. Sentähden ei ulkomailla enään
kaffeeta juodakkaan niinkuin täällä juhlallisena ja halullisena
juomana, vaan sitä nautitaan ruokana, se on: sitä syödään melkein
niinkuin meillä maitoa suuruspalan paineeksi. Ja sitä nauttivat tällä
tavalla köyhimmätkin, työmiehet ja muut. Ei se sillen enää ole heille
mikään herkku, vaan jokapäiväinen tarpeellinen ruoka. Tästä ehkä
arvannee lukia kuinka juuri kaffeen nauttiminen on niissä
valtakunnissa, joissa se on jokapäiväinen elatuksen aine. Tämä
näkyy jo ulkopuoleltakin; sillä niissä paikkakunnissa on joka
kolmannessa talossa kaffehuone, jossa ei ollenkaan muuta saa ostaa
kuin kaffeeta ja jonkun palan sen viereen. Vaikka siis kaffe ei
itsestänsä ole vahingollinen juojille, taitaa se kuitenki niinkuin kaikki
muutkin nautitsemiset tulla vahingolliseksi ylöllisyyden tähden. Ei ole
taivaan kannen alla sitä ainetta, terveellisintäkään, joka ei ylöllisesti
nautittuna tulisi vahingolliseksi. Ja tietty asia on myös että mitä
voimallisempi aine, sitä pikemmin taitaa se myös vahingoittaa.
Senpätähden neuvoisimme omanki maamme kaffejuojia että he
joisivat kaffeensa kuivan ruokapalansa paineeksi, niinkuin tekevät
ulkomaillakin. Ei tosin siitä ole vahinkoa pelättävänä. Mutta toisaalta
on kaffeen ja paloviinan sekoittaminen oikeana myrkkynä pidettävä,
sillä molemmat jo yksinänsäkin ovat väkeviä ja voimallisia aineita.

Toinen on asia, jos kaffe ulkomailta ostettuna on vahingoksi

maallemme. Kysymys on sama jos mikään muu aine, ulkomaalta
tuotuna, on maalle vahingoksi. Kyllä monikin niin luulee, mutta
vähän ajattelemattomasti. Tosi kyllä on että kaikki, mitä ulkomailta
tuodaan, on maksettava; mutta millä se maksetaan? Ei rahalla; sillä
ei paperirahamme siellä kelpaa miksikään ja kulta- ja hopiavuoria ei
meillä löydy maassamme. Kaikki ulkomailta tuodut aineet ovat siis
maksettavat oman maamme tuloilla. Viimisessä kädessä on kauppa
sula vaihetus. Jos taas ajattelemme ulkomaitten ihmisten tilat, niin
havaitsemme että he maksavat meidän maamme kalut heidän
maansa ja työnsä tuloilla. Ellemme nyt ostaisi mitään ulkomailta, ei
kaffeeta eikä muuta, niin arvattavasti eivät taitaisi hekään meiltä
mitään ostaa. Kaikki kauppa olisi tykkänään loppu. Tämän näimme
menneinä vuosina selkeästi; maamme antoi huonon tulon sekä
kuivuuden että hallain vuoksi, josta seurasi ettei talonpoika taitanut
ostaa eikä kauppamies taitanut myydä ulkomaan kaluja muuta kuin
vähän entisen suhteen. Senpätähden ei taitanut kauppamies
ulkomailtakaan tuottaa kuin vähän entisen suhteen. Tämän katsovat
nyt ajattelemattomat hyväksi, koska ulkomaan aineita tuotiin
vähempi maahan kuin ennen. Mutta katsotaaspa toisaaltakin asia.
Suomalaiset toivat vähä ulkomailta, sentähdenpä veivät he myös
vähemmän ulkomaille, taikka oikeammin sanottu: ulkomaalaiset
taisivat myös ostaa vähemmän Suomen kaluja ja tarjosivat
sentähden niistä vähemmän hinnan. Ei ole sentähden Suomen kalut
olleet monena vuonna niin vähässä hinnassa ulkomailla kuin
menneinä. Ja niinpä se on ainakin. Jos vähä myymme ulkomaille,
niin myös ostamme vähän sieltä; taikka takaperin: jos vähän
ostamme ulkomailta, niin myös myymme vähän taikka huonoon
hintaan. Emme sentähden taida sanoa kaffeeta kansan vahingoksi.

Merkillistä on kuinka kaffeen juominen on enennyt siitä kuin sitä

ruvettiin ruokana käyttämään. Yksi ainoa kansa olkoon esimerkkinä.
Vuonna 1808 juotiin Englannissa vaan nimeksi kaffeeta; sinä vuonna
tuotiin sinne yksi miljona naulaa kaffeeta. Vuonna 1832 tuotiin 22
miljonaa naulaa eli 22 kertaa enempi kuin 24 vuotta ennen. Vuonna
1848 tuotiin sinne ja juotiin 45 miljonaa naulaa taikka 45 kertaa
enempi kuin 40 vuotta ennen. Sama on suunta melkein muissakin
maissa.

Mutta vieläkin merkillisempi on se että hinta on samassa määrässä

laskenut kuin nauttiminenki. Vuodesta 1818 vuoteen 1848 eli 20
vuoden kuluessa on kaffeen hinta laskenut enempi kuin puolta
halvemmaksi (eli 65 prosenttia), joka tulee siitä että sen viljelys on
suuressa mitassa enennyt.

Kaikissa paikoissa ulkomailla sanotaan yhteen äänen että kaffeen

juominen on vähentänyt viinan nauttimisen, ja tässä olisi sen suurin
etu. Hallitukset ovatki sentähden aikaa voittain laskeneet kaffetullin
paljo halvemmaksi entistänsä, josta sen nauttiminen on saanut
suuren enenemisen ja siitä syystä tullin tulot valtakunnille antaneet
vielä suuremman voiton kuin ennen.

Jos taitaisimme yhdellä silmän heitolla katsahtaa yli koko sen

suuren liikunnon maailmassa, jonka tämä pieni ja vieras siemen on
matkaan saattanut, kuinka tuhansittain ihmisiä viljelevät ja raivaavat
maita kaffepuita istuttaaksensa, kuinka kauppamiehet niitä sitte
ostelevat talonpojilta ja kokoovat laivain täydet, kuinka laivat merille
sitte niitä kuljettelevat maanpiirin ympäri merimiesten ollessa
vaaroissa, kuinka taas kauppamiehet niitä toinen toisillensa
jakailevat ympäri kaupunkeita, kuinka vihdoin niitä myyvät ostajille
kaikista säädyistä ruhtinoista alkain aina tölliläisten muijihin saakka,
kuin vaskisepät hikoilevat pannua takoissansa ja savenvalajat kuppia
ja muita valaissansa, kuinka akat ja piikat keittelevät tätä herkkua
vartoen sen kiehumista yli laitojen, kuinka viimeiseksi pienet seurat
pakisevat ilossa ja hyvämielissä koska kaffekuppi höyryy nenän alla
— jos kaikki tämän ajattelemme yhteensä ja vielä lisäämme mitä
kaffemyllyt, polttajat ja muut siitä saavat tekemistä, tosin on maan
piirin päällä tuskin mikään yksinäinen aine, joka niin paljon
matkaansaattaa ihmisille toimitusta ja hyvämielisyyttä kuin kaffepuu.

Tupakki.

Kaikkein maailman kasvuin seassa on tupakki merkillisimpiä. Se on

myrkyllinen ja kuitenki nautitsevat sitä melkein kaikki ihmiset yhdellä
eli toisella tavalla. Tästä laveasta nautitsemisesta tulee kohdastansa
se että monet ihmiset sitä kasvua viljelevät ja yhtä monet sitä vielä
kaikin tavoin korjailevat. Jos vielä tähän lisäämme että tällä kasvulla
ei ole syötävää hedelmää eikä juurta eikä muitakaan ravitsevia osia,
että sillä ei ole hyvää hajuakaan, vaan sitä vastoin paha ja karvas
sekä maku että haju, että se nautitessa saattaa oksentamaan ja
pyörtymään ja suuressa mitassa nautittuna tuottaa vielä kuolemanki
[Nikotin on aine, joka saadaan tupakista ja on niin kovin myrkyllinen,
että 4 eli 5 pisaraa kuolettaa koiran], jos kaikki tämän yhteen
ajattelemme, on se sangen merkillistä kuinka semmoinen kasvu on
taitanut ihmisten ja järjellisten ihmisten seassa tulla niin suureen
voimaan kuin sillä nyt ompi. Jos joku olisi pari sataa vuotta
takaperin, koska tupakki vielä kasvoi Amerikan villimetsissä,
sanonut: tuota kasvua tulevat joka maailman maakunnassa ihmiset
kylvämään ja viljelemään, tuota kasvua sitten tuhannet ihmiset
vapriikeissa valmistavat poltettavaksi ja pureskeltavaksi ja nenään
jauhoina pistettäväksi, tuota kasvua kuljettavat tuhannet ihmiset
maitse ja meritse valtakunnasta valtakuntaan, tuota kasvua myyvät
ja ostavat tuhansittain tuhannet kauppamiehet, jos joku pari sataa
vuotta takaperin olisi noin puhunut, eikö häntä todella olisi saanut
hulluksi sanoa? Mutta nyt on tuo kaikki jo tapahtunut. Tupakista sopii
tosin sanoa mitä monesta ihmisestä nähdään, että usein ne tulevat
suureen kunniaan ja arvoon, joista kukaan ei olisi sitä luulla taitanut.

[Tupakki on tosin lääkitykseksikin käytetty, joka on sen ainoa

hyödyllisyys, mutta aivan pieni osa koko tupakin summasta
käytetään lääkkeeksi.]

Viheriäisessä tilassansa on tupakilla aivan vähän hajua ja makua,

mutta kuivassa tilassansa saa tupakki, erinomattain sen lehdet ilkeän
hajun ja aivan karvan maun.

Koska Hispanialaiset ensin tulivat Amerikaan, löysivät he

tnpakkikasvun.
Matkustavaiset Amerikassa kertovat että ihmiset siellä, ennen
Europalaisten sinne tultua, käyttivät tupakkia lääkkeeksi;
erinomattain
oli se aivan hyvä lääke haavoissa.

Myös kertovat ensimäiset matkustavaiset Amerikassa että

Meksikon kuninkaallisessa hovissa oli tapana tupakkia polttaa
kieruissa taikka sigarrina. Koska Englantilaiset ensin tulivat
Amerikaan, löysivät he saman tavan, erinomattain Virginiassa, jossa
vieläkin kasvaa hyvin arvossa pidetty tupakkilai. Europalaisten
näyttää saaneen ensimäisen tiedon tupakista Antillien saaristossa,
sillä nimi Tobako on Haitin kieltä, merkiten sitä putkea, jolla tupakkia
poltettiin, eikä siis itse tupakkia. Tupakin meksikolainen nimi on yete
ja perulainen nimi sagri. Mutta tyhjä luulo on se että tupakin nimi on
otettu Tobago nimisestä luodosta.

Eräs Italialainen Venzoni, joka vuosina 1542-1556 matkusti Länsi-

Indiassa, taikka puoli sataa vuotta jälkeen Amerikan löytämisen,
puhuu laveasti tupakin nautitsemisesta. Ei kauan sen jälkeen,
vuonna 1559, viljeltiin jo tupakkia Lissabonissa lääkitykseksi, ja
senaikuinen franskalainen lähetysmies Portugalissa, nimeltä Nicot,
lähetti tupakin siemeniä sieltä kotimaahansa, erittäin kuningattarelle
Katharina Medici, josta sitä myös Frankriikissa kutsuttiin
kuningattaren yrtiksi. Mutta opillisissa kirjoissa sai se nimen
Nicotiana. Italiassa sai se nimen Herbe de S:t Croix ja Herbe de
Ternabou, sillä Paavin lähetysmies Lissabonissa St. Croix ja
Ternabou, lähetysmies Frankriikissa, lähettivät siemeniä ensin
Italiaan. Vuonna 1586 palasivat muutamat Englantilaiset Virginiasta
ja toivat myötänsä tupakin Englantiin ja yksi niistä, Harriot, sanoo
Englantilaisten oppineen tupakin polttamisen Indianeilta. Pian levisi
tämä polttaminen Englannissa ja pian myös Hollannissa,
Frankriikissa, Spaniassa ja Portugalissa. Hollantiin tuli se tapa
muutamien oppivaisten seurassa, jotka Englannista sinne
matkustivat oppia hakemaan. Myös näkyy tämä tupakin nauttiminen
pian levenneen Turkiaan, Persiaan, Itä-Indiaan, Kinaan ja Japaniin.
Jo vuonna 1601, eli tuskin 50 vuotta jälkeen tupakin ensimäisen
tuomisen Europaan, oli tupakin polttaminen tuttu Kinassa, ja luullaan
sen olevan vieläkin vanhemman Japanissa. Tästä päättävät
muutamat, että tupakki ennen Amerikan löytämistä olisi ollut tuttu
Itä-Aasiassa. He sanoivat että se lai, jota Kinassa viljellään, on
Amerikalaisesta laista erinäinen, ja että se persialainen lai, josta
saadaan se suuresti ylistetty Schiraz-tupakki, on perisukuansa
aasialainen. Mutta toisaalta on suuri syy päättää tämän kasvun
olevan perisukuansa amerikalaisen; sillä koko Aasiassa on sen nimi
tobak, ainoastaan Arabiassa kutsuvat sen nimellä, joka merkitsee
savua. Myös taitaa tapahtua että Kinalaiset, opittuansa Spanialaisilta
tupakkia nautitsemaan, ovat jonkun likisukuisen kotimaan kasvun
täksi nautinnoksi käyttäneet, ja samaten taitaa Persiassakin olla
tapahtunut. Mutta tupakin nauttiminen ja nimi on epäilemättä saatu
Amerikan villikansoilta.

Tupakin nauttiminen on niinkuin kaikki muutkin uudet tavat saanut

kärsiä vastuksia ja vainoja; mutta sillä oli myös puolustajansa ja
levittäjänsä. Merkillinen on Englannin kuninkaan Jaakko I:sen
pilakirja tupakin polttamista vastaan, joka vuonna 1619 tuli ilmi
nimellä Misokapnos. Se on kirjoitettu keskustelemisen tapaan. Siinä
sanoo hän kuinka ilkeä on että ymmärtäväiset ja valaistut ihmiset
ottavat tapoja semmoisilta villikansoilta kuin Amerikan asuvaiset,
että tupakin nautitseminen vahingoitsee terveyden, heikentää
ruumiin voimat, kohmeluttaa järjen, tuo myötänsä riettauden ja
tekee keskinäisen elämän rivoksi; ja että, jos tupakin polttaminen
kasvaa kasvamistansa niinkuin se ruvennut on, vaimojen vihdoin
myös täytyisi tupakkiin turvata koska he eivät muutoin jaksaisi
löyhkäävien miestensä kanssa yhdessä elää. Ja hän päättää kirjansa
seuraavilla kovilla sanoilla: "Sentähden, o kansalaiset, jos teissä vielä
on vähäkin häpyä, niin pankaat pois tuo hullu nautinto, jonka alku
on hävyttömyys, joka tietämättömyydestä on tavaksi otettu, joka
voiton vuoksi levitetään; nautinto, jolla Jumala vihoitetaan, ruumiin
terveys hävitetään, kotoelämä katkerutetaan ja kansan arvo ulkona
sekä kotona häväistään; nautinto, paha silmille ja vielä pahempi
nenälle, aivoille vahingollinen ja keuhkoille kalvavainen; nautinto,
jonka paksut, mustat savupilvet antaa oikean kuvauksen helvetin
kaasusta." Mutta vaikka Jaakko todellakin oli tupakin vihollinen ja
kielsi sen viljelemisen Englannissa, oli tämä kirja kuitenki enimmästä
päästä pilkaksi kirjoitettu. Kuitenki sai se vastustelioita täydellä
todella; sillä muutamat Jesuitat Puolan maalla kirjoittivat sitä vastaan
kirjan Antimisokapnos. Ymmärrettävä on että kuningas Jaakko
saarnasi kuuroille korville. Tupakin polttaminen Englannissa leveni
levenemistänsä erinomaisesti ja vasta viimisen vuosisadan
loppupuolella rupesi se joksikin vähenemään, koska ihmiset
korkeammista säädyistä ei sitä enään pitäneet herrallisena vaan
roistomaisena. Sitte on tupakin nautitseminen Englannissa paljo
vähennyt ja nykyjään nähdään harvoin Englantilaiset polttavan. Joka
siellä kaduilla kulkee, taitaa ainakin sanoa että kukin tupakkia
polttavainen on muukalainen. Alhaisista säädyistä niinkuin työmiehet
polttelevat vieläkin.

Toisaalta kirjoitti eräs Raphael Thorius vuonna 1628 kiitosvirren

tupakin kunniaksi. Samaan aikaan tuomitsi Paavi Urban 8:sas ne
pannaan, jotka kirkossa nuuskua tököttivät naamaansa.

Tupakin nauttimisen suuri ja nopea leveneminen tuli suureksi

osaksi siitä että se helposti käy viljellä melkein kaikissa maissa ja
ilmoissa; eikä sentähden viipynytkään kauan ennenkuin ruvettiin
viljelemään sitä useimmissa Europan, Aasian ja Afrikan maakunnissa.
Mutta monissa maissa tuli sen viljeleminen kiellyksi ja toisissa tehtiin
sille kaikenlaisia esteitä. Aina enemmän tupakin kasvun ja nautinnon
levetessä havaitsivat hallitukset että tästä taidettaisiin saada hyvä
tulo valtakunnalle. Tästä seurasi että tupakki tehtiin valtakunnan
omaksi ja hallitus yksinänsä myi sitä korkeaan hintaan. Tästä taas
seurasi että hallitus kielsi kunkin tupakkia viljelemästä
pakoittaaksensa kunkin tupakkinsa hallituksen myyjiltä ostamaan,
taikka antoi hallitus luvan viljellä tupakkia, mutta viljeliän täytyi
määrättyyn halpaan hintaan myymän viljellyn tupakkinsa; muutoin ei
olisi koko tupakkikauppa tullut hallituksen käsiin. Tämmöinen asetus
on nykyisiin aikoihin ollut voimassa Kuban luodolla ja on vieläkin
Meksikossa. Nämät molemmat ovatki peräti sopivaiset tupakin
viljelykselle. Ainoastaan määrätyillä tiloilla saadaan tupakkia viljellä
ja kaikki tupakki on vietävä hallituksen aittoihin. Hallituksen
lähettiläiset kulkevat ympäri maata ja repivät ylös kaikki tupakin
taimet, jotka luvattomissa paikoissa havaitaan. Näiden on myös
katsominen että kaikki luvallisesti viljelty tupakki tuodaan
hallitukselle. Arvattavasti syntyy tästä paljo lain rikoksia ja riitoja ja
viekoittelemisia.

Muutamissa valtakunnissa on tupakille pantu korkia tulli

maksettavaksi.

Englannin valtakunnassa oli tupakin viljelys kielletty. Toisissa

maissa on tupakin kotoviljelys kehoitettu, niinkuin Pommerissa,
Silesiassa ja muinaan Danmarkissa.

Tupakin viljelys on levinnyt yli suuren osan maan piiriä. Amerikan

useimmat paikkakunnat viljelevät tupakkia, enimmästi kuitenkin
Virginia, Karolina, Venezuela ja Kuba. Englantiin tuotiin vuonna 1831
33 miljonaa naulaa, joista 32 miljonaa oli Amerikasta kotoisin.
Kubasta vietiin vuonna 1840 200 miljonaa sigarria ja noin 3 miljonaa
naulaa lehtiä. Myös Brasiliasta tuodaan paljo tupakkia. Vuonna 1817
vietiin yksinänsä Rio Janeirosta 3 miljonaa naulaa. Europassa
viljellään tupakkia enimmästi Hollannissa, Flanderissa, Elsasissa,
Pfalzissa, Ungarissa, Ukrainissa ja Turkiassa, mutta se tupakki on
arvoltansa halvempi amerikalaista. Keskimeren itäpäässä on tupakin
viljelys oivallinen. Itä-Indiassa ja sen saaristossa viljellään myös paljo
tupakkia. Vielä enemmän viljellään sitä Kiinassa ja Japanissa.
Kapmaahan ja Australiaan on sitä myös nykyisiin aikoihin saatettu.

Keskittäin laskein tuodaan Danmarkkiin vuosittain 2,5 miljoonaa

naulaa tupakkia, josta melkein kaikki on lehtiä, jotka maassa
valmistetaan kaikenlaisiksi tupakkilaiksi.

Jos lasketaan kuinka paljo lehtiä kullekin tupakin laille juoksee ja

siihen lisätään mitä valmistettuna maahan tuodaan, saadaan
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