4466 4470.output

* GB784873 (A)
Description: GB784873 (A) ? 1957-10-16
Improvements in the production of cellulose from lignocellulosic materials
Description of GB784873 (A)
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The EPO does not accept any responsibility for the accuracy of data
and information originating from other authorities than the EPO; in
particular, the EPO does not guarantee that they are complete,
up-to-date or fit for specific purposes.
PATENT SPECIFICATION
Inventors: STANLEY CHARLES BATE and FRANCIS GEORGE PEACHII 784,873
Date of filing Complete Specificai Application Date: Feb 10, 1955.
Complete Specification Published tion: Feb 9, 1956.
No 3999/55.
: Oct 16, 1957.
Index at acceptance:-Class 2 ( 2), W 3 A( 1 A: 1 B: 2 A: 4 C: 11)o
International Classification:-D 21 c.
COMPLETE SPECIFICATION
Improvements in the Production of Cellulose fromw Lignocellulosic
Materials We, BRITISH CELANESE LIMITED, a British Company, of Celanese
House, 22/23 Hanover Square, London, W 1, do hereby declare the
invention, for which we pray that a patent may be granted to us, and
the method by which it is to be performed, to be particularly
described in and by the following statement:This invention relates to
the production from ligno-cellulosic materials, such as woods, straws
and grasses, of cellulose suitable for use as a chemical raw material,
e g for the manufacture of viscose or of organic derivatives of
cellulose such as cellulose esters and cellulose ethers.
A number of kinds of pulping process are known for producing cellulose
from wood and other ligno-cellulosic materials The most important are
the sulphite, soda and sulphate processes in their various forms,

while other processes include chlorination and treatment with nitric
acid, both followed by extraction with alkali The present invention
may be applied to all such pulping processes with the exception of
processes of the sulphite type, i e.
processes in which sulphonic acid groups are introduced into the
lignin, which then dissolves in the cooking liquor.
In all pulping processes economy of the pulping chemicals is to be
aimed at, and this is particularly the case when the pulping chemicals
are expensive, as in the chlorination and nitric acid processes Indeed
although it is recognised that the nitric acid process is
exceptionally suitable for use when cellulose of a high degree of
purity is required for acetylation, it is not under normal conditions
economic owing to the high cost of the nitric acid, and it is doubtful
whether it is today being worked anywhere in the world The present
invention makes possible a considerable reduction in the amount of
pulping chemicals employed in pulping processes of the alkaline type
(soda and sulphate processes), (Price 3 s 6 d 1 chlorination type, and
nitric acid type.
According to the invention, ligno-cellulosic material is given a
pretreatment in which it is subjected first to the action of water at
a temperature above 140 C and then to the action of a hot caustic soda
solution of concentration below 3 %, after which it is subjected to a
pulping process in which the greater part of the lignin originally
contained in the ligno-cellulosic material is removed by alteration by
a chemical reaction other than sulphonation followed or accompanied by
solution of the altered lignin It is found that the combination of
these two pretreatment steps results in the removal from the material
of a substantial proportion of its lignin, though neither step by
itself has any substantial effect on the lignin content of the
material.
The process of the invention may be applied to the production of
cellulose from woods, especially deciduous woods, straws, grasses,
such for example as bamboo and papyrus, and lignin-containing residues
such as bagasse.
Preferably the material to be treated is in a particulate form; thus
wood may be in the form of chips or sawdust, and straws, grasses and
the like may be chopped into small pieces.
In the first stage of the pretreatment the material is heated with
water in a pressure vessel to a temperature above 140 C, especially
between 145 and 155 C Temperatures above 155 C may be used if desired,
but the higher pressures then developed make this economically
undesirable The treatment may last for an hour or more, e g.
for between 1 and 4 hours.
After this treatment the material may be washed, preferably with hot

water, and is then heated with the alkali solution for the second
stage of the pretreatment Preferably a caustic alkali solution of
concentration 0 75-2 5 % is employed, and the ligno-cellulosic
material is heated in this solution to a temperature above 80 or 90 C,
Advantageously it may be boiled in the alkali solution under
atmospheric pressure A pressure boil, e g at temperature up to about
120 C, may be given if desired, but as a boil under atmospheric
pressure is in general perfectly satisfactory it is not economically
desirable to employ pressure The treatment with the alkali solution
may be quite short, lasting for example for about 2 -2 hours, although
it may be extended if desired.
As after the water treatment, so after the alkali treatment it is
desirable to wash the ligno-cellulosic materials, preferably with
water or with a very dilute alkali solution, e g a caustic alkali
solution of concentration up to 3 %, e g between about 0 5 and 3 %.
Material which is to be pulped by a chlorination or nitric acid method
is preferably finally washed substantially free from alkali.
After use the water and the alkali pretreating solution contain a
considerable proportion of organic compounds derived from the
lignocellulosic material In the case of the water the extracted
substances are largely pentosans or hydrolysis products of pentosans,
such as sugars and furfural, which are valuable byproducts and may be
recovered by known methods The alkali solution resulting from the
second stage of the pretreatment is however found to contain not only
pentosans and their degradation products, but also a considerable
proportion of lignin, which can be precipitated by acidifying the
solution By no means all the lignin can be removed from the
ligno-cellulosic materials in this way however long the alkali
pretreatment is carried out, but the proportion which can be removed
is sufficient to reduce to an important degree the consumption of
chemicals in the subsequent pulping operation This is a surprising
fact, since it is well known that a simple treatment with an alkali
solution of such low concentration will not remove any substantial
quantity of lignin Still more surprising is the fact that if the water
treatment is replaced by a boil at atmospheric pressure with a dilute
acid, e g a 1-2 % sulphuric or hydrochloric acid, as in the known
"pre-hydrolysis" operation, the alkali solution is no longer capable
of removing enough lignin to make possible any considerable reduction
in the amount of pulping chemicals used or consumed.
The subsequent pulping operation may be carried out by any known
process other than a sulphite process Owing to the greater cost of the
chemicals employed, the invention is particularly valuable when the
pulping is effected by a chlorination process such as the known
processes associated with the names of Pomrilio and De Vains or the

process exemplified below, or a nitric acid process as described for
example in Specification No.
438,435, or in B I O S Survey Report No.
33, pages 32 and 33 or the process exemplified below The crude
cellulose resulting from the pulping operation may be purified to
reduce its pentosan content still further and to render it
sufficiently pure for conversion into a good quality cellulose ester
or ether or for the production of viscose Suitable methods of
purification involving one or more treatments with alkali and one or
more bleaching operations are well known.
The invention is illustrated by the following Examples.
EXAMPLE I
Woods from a number of different species and in the form of either
chips or sawdust were given the following nitric acid pulping
treatments 80 The chips were added to nitric acid of concentration
suited to the particular wood and in amount sufficient to cover the
chips.
(Different woods require different concentrations of nitric acid for
effective treatment, and 85 in each case the minimum concentration
found to be effective with the particular wood was employed) The
nitric acid containing the chips was then heated for 5-6 hours to a
temperature of 60 -70 C The waste acid 90 was then drawn off as
completely as possible, and an approximately equal volume of water was
added to the chips, heated to 90 -95 C.
for 1 hour, and then run off, so as to remove the greater part of the
nitric acid which still 95 adhered to the chips The chips were then
washed, immersed in a 1 % caustic soda solution and heated in the
solution to 100 C for 1 hour The resulting crude cellulose was then
filtered off and washed 100 Sawdust was treated somewhat differently.
It was mixed with a moderate amount of nitric acid of the minimum
strength found to be effective with the particular wood, and heated
for 4 hours to 60 -70 C At the end of 105 this time the temperature
was slowly raised to 95 C and kept at that level for 1 hour.
The waste acid was drawn off through a filter, and the residue washed
with a little water, the washings being added to the waste acid 110
The treated sawdust was then washed with further water until it was
free from nitric acid.
It was then treated with 1 % caustic soda at 'C as described above.
After each run, either with chips or with 115 sawdust, the recovered
nitric acid solution was made up to the required strength and employed
again.
Two sets J, trials were made, one on wood which had not been given any
pretreatment, 120 and one on wood which had first been heated with
water to 150 C for two hours and then boiled under atmospheric

pressure with a 10 caustic soda solution for one hour The results
obtained with and without a pretreatment 125 are shown in the
following table, 784,873 784,873 Sycamore chips A B Spruce chips A B
Spruce sawdust A B 97.8 98 0 10.7 10.0 5.6 7.0 99.2 98 1 4.7 3 5 15.0
15 0 96.5 96 9 5.2 3.9 15.0 15 O Nitric acid consumed (% on dry weight
of wood) 27.5 13.7 52.8 40.6 42.4 36 7 Oak sawdust A B Ash sawdust A B
Cellulose in product (%) Pentosan in product (%) Strength of nitric
acid used (%) Nitric acid consumed (% on dry weight of 97.0 98 7 12.2
8.0 32.8 2.8 8.0 11.6 96.4 97 6 12.7 6.5 14.7 5.7 6.5 8.5 A = No
pretreatment B = Two-stage pretreatment described above The figures
given in this Table and that in Example 2 for "Cellulose in product"
("H-olocellulose") were obtained by subjecting the product to
alternate treatments with sodium chlorite and sulphite The pentosans
were determined by the phloroglucinol method.
It will be seen that in all cases the amount of nitric acid consumed
was considerably less when the wood had been given the two-stage
pretreatment than when it had not, the effect being particularly
marked with the deciduous woods At the same time the wood which had
been given the pretreatment gave a crude cellulose of a lower pentosan
content than the untreated wood It is probable that the relatively
small advantage apparent with the conifer spruce is due to the fact
that coniferous woods have in general a smaller pentosan content than
deciduous woods.
EXAMPLE II
Sawdust of different wood species was suspended in water, and 5 %
hydrochloric acid and a bleaching liquor containing 2 % available
chlorine added simultaneously while the suspension was stirred The
addition of the two chemicals were so made that the liquor was always
acid, though the acidity did not exceed 0 05 % hydrochloric acid at
any time.
The addition was continued as long as chlorine was absorbed The wood
was then filtered off and washed, after which it was stirred for half
an hour with a dilute caustic soda solution containing about 8 % of
caustic soda on the weight of the wood The crude cellulose so obtained
was washed, and then given a further standard alkali purification
treatment.
The results obtained with and without a pretreatment as described in
Example I are summarised in the following table.
Cellulose in product (%) Pentosan in product (%) Strength of nitric
acid used (%) 784,873 Ash A B Oak A B Chlorine consumed (% on wt of
wood) Cellulose in crude product (%) Pentosan in crude product (%)
Yield of cellulose after further purification (% on wt.
of wood) Pentosan in purified cellulose (%) 44.4 22.8 92.6 96 0 21.9
10 1 39.1 33 8 10.9 60.0 22 5 90.6 96 2 22.5 5.7 38.5 26 4 1.4 68.0 63

4 87.6 94 0 6.7 3.9 9 - 1 3 A = No pretreatment B = Two-stage
pretreatment described above, in Example I.
As will be seen, with the conifer spruce the consumption of chlorine
was reduced to a much smaller extent than with the deciduous woods,
though even so the consumption of chlorine was reduced by nearly 7 %
Moreover the crude cellulose obtained by chlorinating the untreated
spruce was highly impure, and could not easily be made to give a
useful product even when subjected to a further alkali purification.
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* GB784874 (A)
Description: GB784874 (A) ? 1957-10-16
Improvements in and relating to high-tension electric discharge tubes
PATENT SPECIFICATION
Date of filing Complete Specification July 27, 1955.
Application Date March 22,1955.
784,874 No 8308155.
I / / Complete Specification Published Oct 16, 1957.
Index at Acceptance: -Class 39 ( 1), D( 9 A: 12 A: 35).
International Classification HO 1 j.
Improvements an End relating to l High-Tenssion Electric Discharge
Tubes I, ELLIS WALLACE ELLIS, a British Subject, of 24, Marshalsea
Road, London, S E 1, do hereby declare the invention, for which I pray
that a patent may be granted to me, and the method by which it is to
be performed, to be particularly described in and by the following
statement: -

This invention relates to high-tension electric discharge tubes having
a gas filling (more particularly argon) and mercury vapour, utilised
for advertising signs, interior, and other lighting, and similar
purposes, of the type in which a chamber situated at each end of the
tube and which contains a supply of liquid mercury and houses the
electrode, electrode support wires and pinch or seal, at that end, is
formed or provided with means to comprise a mercury trap, to
constitute an impediment of such character that it retains the mercury
in the chamber but allows the mercury vapour (which is necessary to
give blue light) to pass into the tube and carry out its function.
According to the present invention the impediment for trapping the
mercury comprises a cylinder of mica, preferably bent from a
rectangular sheet, one end of which fits into the end of the tube at
its junction with the electrode containing chamber and the other end
of which projects a desired extent into said chamber.
In most cases an electrode-containing chamber is of elongated
cylindrical form with a pinch or seal at one end for the electrode
support wires leading to the electrode and for holding the electrode
(of hollow cylindrical or other form) in position and in line with the
axis of the tube at its junction with the other end of the chamber.
In order that the invention may be better understood, it will now be
described with reference to the accompanying drawing which is
diagrammatic and given by way of example only and in which:Fig 1 shows
an electrode for a high tension electric discharge tube having a
mercurytrapping impediment, made in accordance with the invention, in
sectional elevation.
Figs 2 and 3 are details relating thereto.
lPrice 3 s 6 d l In carrying the invention into effect as shown in
Figs 1 to 3, a small rectangular 50 sheet 6 or mica (Fig 2) of
adequate dimensions, is rolled into a cylinder 11 with the ends
overlapping to a desired extent (Fig 3) and this is fitted (as shown
in Fig 1) into the end of the discharge tube 7 at its junction with 55
the electrode chamber 8 which is of larger diameter, so that the said
mica tube projects into the hollow electrode 9 It may, however, stop
short of the said electrode.
Between this mica impediment and the 60 sealed end 10 of the chamber
8, a desired amount or " blob " 12 of mercury is located.
It will be understood that with the electrodecontaining chamber 8 in a
horizontal or other position, the impediment formed by the por 65 tion
of the cylinder 11 projecting from the tube 7 constitutes a mechanical
means which acts to trap the mercury and overcome its migration On the
other hand, it forms no impediment to the free passage of the mercury
70 vapour evolved during the operation of the tube.

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* GB784875 (A)
Description: GB784875 (A) ? 1957-10-16
Improvements in table game or deck or floor game apparatus for use in
playing a table or deck or floor game
PATENT SIPECIFILCA Tio N
> 78 /A j @ /e Date of filing Complete Specification March 19, 1956.
tg__ -Application Date March 28, 1955 No 8933 Complete Specification
Published Oct 16, 1957.
Index at Acceptance:-Class 132 ( 2), H 6 (A 1: F 9: Fll: F 12), I 1 H.
International Classification: -A 63 b, d.
Improvements in Table Game or Deck or Floor Game Apparatus for use in
Playing a Table or Deck or Floor Game I, SYDNEY WEBSTER, 111,
Aldermans Green Road, Coventry, Warwickshire, British subject, do
hereby declare the invention, for which I pray tfat a patent may be
granted to me, and thile method by which it is to be performed, to be
particularly described in and by the following statement: -
The present invention relates to improved table game or deck or floor
game apparatus in which balls are rolled, flicked, or propelled
mechanically or otherwise along the length of a playing surface with
the object of striking and knocking down suitably shaped pins of wood
or othler material which are set up on end for the purpose in a
predetermined pattern at one end of the playing surface By the word
"pins" as herein used are meant cojcc;s approximating substantially in
appearance to the characteristically shaped pegs or pins used in the
game of "slittles" The present invention is intended to provide an

improved game of the "skittles" class inasmuch as it offers novel
scope and reward for the exercise of skill and observation on the Fart
of players The invention is particularly characterised in that
although all the pins of a set are substantially identical in
appearance when set up for play certain but not all of them are so
weighted and balanced, or are made of heavier material than the rest,
or are otherwise more or less secured in an upright position chat they
are less likely to or do not fall over when struck by suitable balls
during the no:inal playing of the game, and that the only person who
initially knows the positions of the specially weighted or secured
pins is the person who set them up When a ball strikes one of the
"special" pins it rebounds therefrom in a characteristic way, and it
is for the player who is then in play to try to discover the
whereabouts of the special pins by close observation of the shots he
makes The nature of the game of the invention is such that the
apparatus relating to it may be made in various sizes, but in fact one
of the objects of the invention is to provide a game of the type set
forth which may conveniently be played in small rooms or in other
places where there is little space According to this invention a table
or deck or floor game of the type 50 referred to comprises a set of
preferably nine skittle-type pins which when set up for play are in
appearance substantially identical but of which preferably three are
so constructed that they do not normally fall when struck by the 55
balls used in the game; a proportionately long and narrow table or
board having a proportionately short section of preferably cushioned
fixed or movable deflection rail at each of its long sides and
appropriately having suitable 60 holes in which special pins may be
inserted, and further an independent spring plunger gun appropriately
provided with swivel or slide and swivel mounting In order that this
invention may be clearly understood and 65 readily carried into effect
drawings are appended hereto illustrating embodiments thereof, and
wherein:Fig 1 is a perspective view showing the table or board fitted
with deflection rails; a set 70 of nine pins set up at the appropriate
end of the board, and a barrier for stopping balls comprising a net
fastened to posts; Fig, 2 is a plan view of Fig 1; Fig 3 is a view of
a pin; 75 Fig 4 is a view of a pin having an extended portion at its
base forming a supporting peg; Fig 5 is a broken detail sectional view
of the pin shown in Fig 4; Fig 6 is a broken detail perspective view
80 showing holes near the appropriate end of the board for
accommodating the supporting peg of the type of pin shown in Figs 4
and 5; Fig 7 is a detail longitudinal elevation view of a spring
plunger gun; 85 Fig 8 A is a longitudinal elevation view of a spring
plunger gun fitted with a swivel peg mounting; Fig 8 B is a broken
detail sectional plan view of the table or board showing holes in

which 90 gun mounting shown in Fig 8 A fits; Fig 8 C is a broken
detail sectional elevation view showing a hole for gun mounting; Fig 9
A is a longitudinal elevation view of 4,875 555.
a spring plunger gun fitted with a slide and swivel mnounting; Fig 9 B
is a broken detail sectional plan view of the table or board showing
the slot in which the slide and swivel mounting operates; Fig 9 C is a
broken detail sectional elevation view showing view of the
inverted-T-shaped slot in which the slide and swivel mounting
operates; Fig 10 is a detail perspective view showving swivel mounting
on the underside of the gun block; Fig 11 is a detail perspective view
showing a slide and swivel mounting on the underside of the gun block.
Referring to the drawings the table or board 1 is proportionately long
and narrow and is equipped with a proportionately short section of
preferably cushioned fixed or movable deflection rail 3 at each of its
long sides The board or table may be made of wood, hardboard, plywood,
blockboard, plastic material, or any other suitable material, and the
surface is preferably covered with baize or similar cloth or may be
flock-sprayed A starting or base line 4 is marked across the board
near one end and suitable balls are propelled from positions on or
behind this line The area at that end of the board remote fromr the
starting line is marked according to a predetermined pattern with
spots on which pins 5 are set up for play By this means the pins 5 may
be set up consistently in the proper positions without waste of time
Instead of the said spots holes 7 of suitable diameter may be bored in
the board as shown in Fig 6 These holes are necessary when special
pins having peg-like extensions 6 at the base are to be used in the
game instead of specially weighted pins The purpose of the deflection
rails 3 is to allow extra latitude in the provision of means for
making extraordinary angle shots For example a player may propel a
ball so that it first strikes a deflection rail and then rebounds
therefromi at an angle calculated to cause it to strike one or more
pins in a manner advantageous to the player It has been found that by
this means pins may be struck at angles not normally possible with
more direct shots aimed along the length of the board A low net 2 or
other barrier made of cloth or any suitable material is provided for
checking and stopping balls as they run off the table or board If a
more elaborate and expensive arrangement is preferred a fitted or
loose ramp with stopping barrier may be provided The ramp borders the
board for about two thirds of its extent and is so sloped that any
ball arrested by it is delivered back to a point near the playing end
of the board at one side or the other A set of pins 5 made of wood or
any other suitable material are preferably of the shape shown in Fig 3
but they may alternatively be any adaptation of a bottle or cigar or
the like shape having such actual proportions and balance as will

allow of standing evenly upright when placed on end upon a
substantially flat and even surface The preferred set comprises nine
pins which iwhen set up for play are substantially alike in appearance
but particularly 70 characterised however in that at least and
preferably three of them are specially weighted and balanced or are
otherwise distinctively constructed so that they are less likely to or
do not fall over when struck by balls in the course of 75 play These
weighted or otherwise distinctively constructed pins are referred to
herein for the sake of convenience as "special" pins.
In a set of nine pins thereare preferably three so-called special pins
The outstandingly novel 80 feature of the set of pins of the invention
is that during play the special pins can only be detected by handling
them or observing effects when they are struck by blls It is therefore
apparent that at the start of a game only the 85 person who actually
sets up the pins for play is aware of the positions of the special
ones.
The player vwho propels the balls must closely obserre the effects of
his first shots in order to discover the whereabouts of the special
pins 90 so that he may ail subsequent shots only at the others In a
modification all the pins comprising a set are substantially identical
both in appearance and weight but at least three of them are
characterised as special pins in that 95 they nave a concealed
magnetised or magnetisable plate fitted at the base The table or board
for use with these pins is anppopriately adapted by the provision of a
suitable section of magnetised or non-magnetisable material 100
incorporated in the playing surface of the board at the apprqopriate
end thereof Referring now particularly to the special pin shown in Fig
4 it will be noted that the base of this is extended at a reduced size
to form a sup 105 porting peg 6 whicl is shown in more detail in Fig 5
Preferably three such pins are included in a set of nine pins and when
set up for playv 'he pegs of the special pins are inserted optionally
in any of the holes 7 as 110 p.ov i d by the imodification of the
board 1 shown in Fig 6 The rest of the pins are set up so that all the
holes are then concealed, this being neatly effected since the holes
are of lesser diamleter than the base of the pins 115 In this way the
basic principal of the game remains unchanged in that the special pins
with base pegs do not fall over when struck by balls, and also in that
the person who sets up the pins may by dint of exercising a modi 120
cum of concealment do so without anyone but himself knewing the
positions of the special pins Pegs at the base of pins are preferably
round but nmay be of any desired shape to fit corresponding holes in
the board In the 125 game of this invention balls may be propelled by
rolling, flicking with finger and thumb striking with a cue, or by the
use of a mechanical striker The apparatus of the invention includes a

mechanical striker of which an 130 784,875 184,8 " 5 embodiment is
showvn in Fig 7 This is an independent spring plunger gun comprising a
gun barrel 9 secured to a gun block 8 both being suitably bored to
accommodate the plunger 10 which is pulled back by hand to compress
the spring 1 OA When the plunger is released the striker end of this
hits a ball which has been placed in an appropriate position for the
purpose and which is then driven according to the direction in which
the gun has been aimed The gun is not secured to the board and is held
in position by one hand whilst the plunger is operated by the other.
The component parts of the gun may be made is of wood with the
exception of the spring or they may be made entirely of metal Figs SA,
8 B, and 8 C illustrate a modification wherein the gun is provided
with a swivel mounting 11 consisting of a cylindrical peg centrally
secured to the underside of the gun block 8 which corresponds with and
may be engaged in any one of a row of holes 12 sited appropriately
near the starting end of the board 1 In this modification the gun may
be readily swivelled to any required angle and lateral movement of the
gun is obtained by moving it from hole to hole as needed A more
elaborate mounting arrangement is provided by the modification shown
in Figs 9 A, 9 B, and 9 C This is a slide and swivel mounting A
similar but shorter cylindrical peg as already described terminates in
a disc 13 which corresponds to and slides and turns within the limits
of an inverted-T-shaped slot 14 at a suitable distance from the
starting end of the board 1.
A feature of this modification is that the open end of the
inverted-T-shaped slot may be secured in any suitable way when the gun
is mounted This means that the gun could not be removed so long as the
slot renmained secured If desired this type of slot may be arranged
upon the actual surface of the board by the provision of suitable
slats of wood or metal By means of the present invention a highly
entertaining game is provided which offers very considerable scope for
careful observation and the exercise of manual skill, and wherein
points are scored for knocking down those pins which in the nature of
the o game are intended to be knocked down when struck appropriately
by suitable balls in the course of play A feature of the invention is
that a satisfactory game may be provided when only part of the
apparatus is used For example the type of pins shown in Fig 3 of the
drawings wherein the special pins comprise specially weighted ones may
be used on any suitable and reasonably level surface such billiards or
bagatelle table, a carpeted or uncarpeted floor, or in a skittle alley
or sports arena, and balls used therewith may be rolled, flicked,
struck by a cue, or propelled where appropriate by the independent
spring plunger gun of this invention.

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* GB784876 (A)
Description: GB784876 (A) ? 1957-10-16
Improvements in or relating to lubricants
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The EPO does not accept any responsibility for the accuracy of data
and information originating from other authorities than the EPO; in
particular, the EPO does not guarantee that they are complete,
up-to-date or fit for specific purposes.
PATENT SPECIFICATION 784,876
Date of Application and filing Complete Specification March 29, 1955.
No 9200/55.
A oplication made in France on April 13, 1954.
Complete Specfication Publis'hed Oct 16, 1957.
:ceptance:-Class 91, F 1.
al Classification:-Cl Om.

COMPLETE SPECIFICATION " Improvements in or relating to lubricants "
We, REGIE NAT 1 ONALE DES USINES RENAULT, of 8/10, Avenue Emile Zola,
Billancourt (Seine), France, a Company duly organized under the laws
of France, do hereby declare the invention, for which we pray that a
patent may be granted to us, and the method by which it is to be
performed, to be particularly described in and by the following
statement: -
The present invention relates to lubricants.
The lubrication of mechanical elements is most generally effected by
the hydrodynamic entrainment of the oil, which interposes a film of
oil between the metal surfaces which are subjected to relative
movement with respect to one another.
It is known that, when the pressure which forces the surfaces against
one another becomes too great, the hydrodynamically entrained film of
oil is broken and that it is possible to interpose an organic film,
resistant to high pressures, between the metal surfaces by the action
of chemically active fatty materials which adhere strongly to the
surfaces and are disposed in thin and oriented layers.
It is known that the so called unctuous films thus constituted
disappear when the working temperature rises to a value greater than
that of the melting point of the iron soaps corresponding to the fatty
acid, this temperature being a moderate one of the order of 75 'C and
in most cases less than the temperature generally attained by the
actual mechanisms used in industry and in motor vehicles.
It is known that when the pressure increases beyond that at which the
unctuous friction is ensured or when a considerable amount of slipping
raises the contact temperature, the fatty film also disappears and it
is necessary to resort to the so called "extreme pressure" additives
which generally contain chlorine, sulphur or phosphorus and which
ensure, in severe friction conlPrice 3 s 6 d l ditions, the
interposition of a non-metallic film between the bearing surfaces.
It has not so far been possible to prepare universal lubricants
possessing at the same time the properties of unctuosity ensuring 50
the provision of an unctuous film at moderate pressures or
temperatures and preventing seizing from taking place when the loads
or the amount of slipping are very great In severe friction conditions
the needs 55 have been met with sulphurised and chlorinated materials
of the "extreme pressure" types, so that if unctuosity is not ensured
the friction temperature under moderate loads rises in such a manner
that the extreme pres 60 sure additives finally come into action,
their activity being perceptible as soon as the temperature reaches a
certain value.
But this temperature necessary for their action may only be reached
after the parts 65 have undergone some irremediable damage; this is

particularly the case with new mechanisms where, owing to
irregularities in machining and assembly, very variable moderate or
very strong pressures are en 70 countered at various points It is
important for the efficient later use of these mechanisms that
running-in by abrasion or deformation shoufld take place gradually
without any seizing or tearing of the metal taking place 75 In an
attempt to raise the critical temperature at which the unctuous
lubricant ceases to act, fatty materials of high molecular weight have
been incorporated in lubricating oils, those fatty materials having as
high a 80 number of carbon atoms as possible in order to raise the
melting point of the corresponding soap The preparation of these
materials was very much hindered by the small number of suitable
natural raw materials 85 available, since the most common natural
materials contain but 18 carbon atoms, and by the difficulty of
syntheses Moreover, in order to increase the range of action of the
lubricant against pressure, it was quite 90 Index at Ac Internation
naturally proposed to mix the extreme pressure additives and the
unctuous -materials together, but when these mixtures are made it is
found that the unctuous properties of the fatty esters are totally or
partially inhibited.
Lubricants have now been found whose unctuosity ensures a very low
co-efficient of friction and which maintain this unctuosity at a much
higher temperature than do hitherto known lubricants.
Furthermore the new lubricants have the remarkable property of both
being unctuous and at the same time of ensuring resistance to seizing
under strong pressure The lubricants according to the invention are
obtained by mixing in certain proportions with mineral oils or any
other oleaginous mixture of chemically inert hydrocarbons, obtained
for example by the distillation of coal, a long chain aliphatic ester
of a fatty acid, said ester having a number of carbon atoms greater
than 12 and a straight chain aliphatic ester of a fatty acid
comprising 4 halogen atoms of which 3 are fixed to the chain end
remote from the esterified carboxyl group and 1 in position 2 with
respect to the halogenated terminal group Methyl tetrachlorolaurate C
13 C CH 2 CHC 1 (CH)8 CO 2 CH, is particularly suitable: it has the
great industrial advantage that it can be prepared easily, and with a
high efficiency, from undecylenic acid which is itself obtained
industrially by cracking castor oil; the reaction is carried out with
a good yield when carbon tetrachloride is caused to react on
undecylenic acid in the presence of benzoyl peroxide acting as a
catalyst.
According to the present invention there is provided a lubricant
comprising the blend of mineral oil, or any other oleaginous of
chemically inert hydrocarbons, with long chain aliphatic esters of

fatty acids, said esters having more than 12 carbon atoms in the
molecule and constituting between 0 2 % and 2 0 % of the lubricant,
and aliphatic esters of fatty acids containing in the molecule, 4
halogen atoms of which three are attached to the end of the chain
remote from the esterified carboxyl group and one in position 2 with
respect to the end halogenated group, said halogen-containing esters
constituting between 0 1 % and 2 0 % by weight of the lubricant.
The properties of the lubricant of the invention are revealed by
laboratory measurements of the coefficient of friction at a mean
contact pressure of 15 kg/mm 2 made on the Herschel apparatus wherein
three balls are rotated by contact with a metallic disc turning in its
plane about its axis.
The driving torque of the balls, proportional to the co-offlicient of
friction, is measured by opposing thereto the torque of a spiral
spring When the balls are wetted with a pure mineral oil there is no
stable position of the needle connected to the opposing spring There
is a rapid succession of dry drive and of lubricated friction The 70
co-efficient of friction varies between 0 15 and 0 19 The friction
becomes stable when the oil contains either a fatty ester or the
mixture according to the invention, but in the first case stability
disappears at a lower 75 temperature than in the second case.
The co-efficients of friction and their variations as a function of
temperature are represented in the curves in Figs 1 to 9 of the
accompanying drawings Each curve 80 represents the variation of the
co-efficient of friction as a function of time (in minutes) in one
experiment, the experiments varying from one to the other in
temperature or nature of lubricant The viscosity of the oils 85 used
was 12 centistokes at 50 WC.
Figs 7 to 9 inclusive concerns a known mixture of 1 % methyl stearate
in mineral oil, the viscosity being 12 centistokes at 50 WC The curves
of Figs 1 to 6 relate to a mixture 90 according to the invention
containing mineral oil, 1 % methyl stearate and 0 2 % methyl
tetrachlorolaurate Finally, Fig 10 of the accompanying drawings
represents the variation of the co-efficient of friction as a 95
function of temperature in the case of each of these two mixtures.
The division of each curve of Fig 10 into two branches takes place at
the instant when the friction becomes non-uniform and there 100 fore
the entrainment of the balls by the plate becomes irregular and
results in an oscillatory phenomenon It appears clearly that while,
with lubricants containing the known fatty esters, all unctuosity
disappears at 105 about 75 CC, this unctuosity still persists with the
lubricants according to the invention as far as 115 'C This is
particularly valuable in practice since the working temperature of
very numerous mechanisms lies within the 110 range 75 o C-115 'C.

The resistance to seizing under heavy loads is shown by the
measurements made on the Boerlage 4-ball machine, wherein the pressure
amounts to between 250 and 500 115 kg/mm 2, with lubricants containing
fatty esters whose use was already known and with lubricants according
to the invention.
The curves in Fig 11 of the accompanying drawings show the variation
of the seiz 120 ing delay in seconds in the Boerlage machine, as a
function of the load in kilograms; the curve corresponding to a
mixture according to the invention containing mineral oil, 1,' methyl
stearate and 1 % methyl tetrachlo 125 rolaurate and having a viscosity
of 47 6 centistokes at 50 WC, is close to the mean curve which would
be obtained with most good commercial oils blended solely for the
purpose of providing protection against seizing 130 at all pressures
but having no unctuous property.
The mixture according to the invention mentioned in connection with
Fig 11 con784,876 porating, in already prepared lubricants having a
basis of mineral oil or other oleaginous 50 mixture of chemically
inert hydrocarbons, the already described tetrahalogenated esters in
proportion of between 1 to 8 % Such lubricants are able to ensure the
regular running of hypoid gears for example 55
* Sitemap
* Accessibility
* Legal notice
* Terms of use
* 5.8.23.4; 93p
* GB784877 (A)
Description: GB784877 (A) ? 1957-10-16
Improvements in or relating to ornamental beads
We, CHELTON (Po P Piis) LIMITEP, a
British Company, and WILLIAM TROUTBECK SANDERSO Ni, a British Subject,

both of Spittall Square, Marlow, Buckinghamshire, do hereby declare
the invention, for which we pray that a patent may be granted to us,
and the method by which it is to be performed, to be particularly
described in and
by the following statement:-
This invention relates to ornamental beads such as are strung together
to form a necklace, bracelet or the like.
When beads are strung together on a cord, the cord has to be knotted
between each bead in order to prevent the beads from all falling off
the cord if the latter should break.
Such knotting of the cord between the beads is a laborious process and
increases the cost of manufacture of a string of beads.
It is an object of the present invention to provide a construction of
bead which can be strung on a cord but which will obviate the need for
knotting the cord between the beads.
According to this invention, an ornamental bead having a bore through
which is to be passed the cord on which the bead is to be strung is
characterised in that the bead is formed of resilient plastic material
and has at least one web or lug extending across or into the bore, the
web or lug being sufficiently thin that it can be pierced by a needle
carrying the cord The cord is gripped by the resilient plastic
material of the web or lug and thus the bead is prevented from
slipping along the cord It will thus be seen that, if the cord should
break, the beads will not fall off.
The bead may be moulded from polythene and conveniently is formed as a
single moulded unit.
Most conveniently, the web extends over the whole cross-sectional area
of the bore thereby ensuring that a needle inserted lPrice 3 s 6 d l
through the bore must pass through the web.
With such a construction, to enable the bead to be moulded as one
unit, one such web would be provided across the bore The web may
extend across the bore normally to the axis thereof, but, as explained
below, it may in some cases be preferable to make the web lie in a
plane sloping across the bore at an angle to the axis thereof.
The invention also includes within its scope a necklace formed of
beads as described above, the beads being strung on a cord passing
through the bore of each bead, the holes for the cord in the webs or
lugs having a diameter sufficiently small to grip the cord.
The following is a description of one embodiment of the invention,
reference being made to the accompanying drawings in which: Figure 1
shows part of a necklace with one of the beads in section; and Figure
2 shows, in section, another form of bead.
In Figure 1, there are shown a number of beads such as 10, 11 and 12
which are strung on a cord 13 The beads are all formed liy a moulding

process from polythene and, as is seen from the drawing of bead 11
which is shown in section, the beads have a diametral bore 14 across
which extends a web 15 moulded integrally with the bead Most simply
and most conveniently this web extends across the whole sectional area
of the bore but it may, if desired, be in the form of a narrow strip
extending across a diameter of the bore or a lug projecting from the
bore wall The beads are strung on the cord 13 by threading the cord on
a needle and by then passing the cord through the webs 15 of the
various beads with the aid of the needle which is used to pierce a
hole in each web 15 Due to the resilience of the polythene, the holes
in the 784,877 PATENT SPECIFICATION
Date of filing Complete Specification: Feb 6, 1956.
By Application, Date: April 4, 1955 No 9737/55.
Complete Specification Published: Oct 16, 1957.
Index at Acceptance:-Class 43, H( 1 X: 7).
International Classification:-A 44 c.
COMPLETE SPECIFICATION.
Improvements in or relating to Ornamental Beads.
65.
784,877 webs 15 made by the needle tend to close onto the cord 13 and
will therefore grip the cord If for any reason the cord should break,
due to the webs gripping the cord, the beads will not fall off the end
of the cord There is thus no need to knot the cord between the beads
as is the normal practice when stringing beads together.
In Figure 2 there is shown an alternative construction of bead 20
having a diametral bore 21 with a web 22, this web lying in a plane
sloping across the bore at an angle to the axis thereof This
arrangement has the advantage that the additional length and
inclination of the web provides a better grip on the cord than does
the arrangement of Figure 1 where the web is at right angles to axis
of the bore, and this permits the use of material of less resilience.
* Sitemap
* Accessibility
* Legal notice
* Terms of use
* 5.8.23.4; 93p

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