U.S. patent application number 11/831116 was filed with the patent office on 2008-01-24 for multiautoclave with set of vessels for combinatorial synthesis of zeolites and other materials.
Invention is credited to Brent J. Anderson, Maureen L. Bricker, Ralph D. Gillespie.
Application Number | 20080020944 11/831116 |
Document ID | / |
Family ID | 38971637 |
Filed Date | 2008-01-24 |
United States Patent
Application |
20080020944 |
Kind Code |
A1 |
Anderson; Brent J. ; et
al. |
January 24, 2008 |
Multiautoclave with Set of Vessels for Combinatorial Synthesis of
Zeolites and Other Materials
Abstract
A vessel arrangement having a base and multiple vessels suited
for simultaneously conducting a plurality of isolated experimental
reactions or treatments at atmospheric process conditions or
elevated temperatures and pressure condition has been developed. A
component of a first material is introduced into one independent
vessel through an opening in its top of the first vessel and
another component of a second material is introduced into a
different independent vessel through its top. Both vessels are
removably located about a base at different first locations.
Transformation of the components in the vessels then occurs to
produce different materials therein. After completion of the
experiments a displacement medium simultaneously urges the vessels
from their respective locations about the base for discard or reuse
after any necessary cleaning. Typically at least one property of
the materials from the vessels is determined either within the
vessel or after recovery of the materials.
Inventors: |
Anderson; Brent J.;
(Palatine, IL) ; Gillespie; Ralph D.;
(Friendswood, TX) ; Bricker; Maureen L.; (Buffalo
Grove, IL) |
Correspondence
Address: |
HONEYWELL INTELLECTUAL PROPERTY INC;PATENT SERVICES
101 COLUMBIA DRIVE
P O BOX 2245 MAIL STOP AB/2B
MORRISTOWN
NJ
07962
US
|
Family ID: |
38971637 |
Appl. No.: |
11/831116 |
Filed: |
July 31, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10834648 |
Apr 29, 2004 |
|
|
|
11831116 |
Jul 31, 2007 |
|
|
|
Current U.S.
Class: |
506/32 |
Current CPC
Class: |
B01J 2219/00484
20130101; B01J 2219/00599 20130101; Y10T 436/11 20150115; Y10T
436/113332 20150115; B01J 2219/00754 20130101; Y10T 436/25
20150115; Y10T 436/114165 20150115; B01J 19/0046 20130101; B01J
2219/00585 20130101; B01J 2219/00747 20130101; B01J 2219/00601
20130101; B01J 2219/00495 20130101; B01J 2219/00333 20130101; B01J
2219/00596 20130101; B01J 2219/00283 20130101; B01J 2219/00477
20130101 |
Class at
Publication: |
506/032 |
International
Class: |
C40B 50/18 20060101
C40B050/18 |
Claims
1. A method of making an array of materials in quantities suitable
for research and development experiments comprising: a) introducing
at least one component of a first material into an independent
first vessel through a top opening of the first vessel; b)
introducing at least one component of a second material into an
independent second vessel through a top opening of the second
vessel; c) removably locating the independent first vessel about a
first opening in a framework at a first location for contact of a
first portion of the vessel with the framework and removably
locating the independent second vessel about a second opening in
the framework at a second location for contact of first portion of
the second vessel with the framework; d) positioning a first
trapping surface for contact with a second portion of the first
vessel when the first vessel is located in the framework and a
second trapping surface for contact with a second portion of the
second vessel when the second vessel is located in the framework;
e) urging the first and second trapping surfaces in unison into
contact with the first and second vessels to create trapping
contact between the first and second vessels and the framework
thereby fixing the location of the first and second vessels
relative to the framework; and, f) urging the first and second
trapping surfaces out of contact with the first and second vessels
to permit withdrawal of the first and second vessels from the
framework.
2. The method of claim 1 wherein the framework is provided by a
base and the base defines bores that retain the vessels and a least
a portion of the bore provides the first trapping surface.
3. The method of claim 1 wherein the first and second trapping
surfaces move in opposite directions along parallel paths to engage
the vessels.
4. The method of claim 2 wherein the second trapping surface
comprises a retaining plate that covers the open end of the
vessels, clamping of the retaining plate over the base engages the
plurality of vessels and optionally the tops of the vessels extend
above the bores and pressure from the retaining plate seals the
interior of the vessels.
Description
CROSS REFERENCE TO THE APPLICATION
[0001] This application is a Division of copending application Ser.
No. 10/834,648 filed Apr. 29, 2004, the contents of which are
hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to a vessel arrangement having
a base and multiple vessels suited for simultaneously conducting a
plurality of isolated experimental reactions or treatments at
atmospheric process conditions or elevated temperatures and
pressure condition.
BACKGROUND OF THE INVENTION
[0003] In recent years, new, automated methods for the systematic
preparation of new compounds, so-called "combinatorial techniques"
have been developed. A wide variety of methodologies, tools and
techniques wear the label of combinatorial methods. Generally these
methods seek to accelerate the discovery of new materials and the
application of new and known materials to new uses by increasing
the number and rapidity of material tests though reductions in the
size of material samples. A particular type of combinatorial
methods focuses on the creation and/or analysis of arrays of
materials at discrete locations on a substrate of some type. The
substrates often comprise a base having regions defines by
depressions, wells, walls of other structural means to separate the
regions and keep the different materials in the arrays isolated for
synthesis and analysis.
[0004] The size of the materials samples in the regions are of
necessity kept small to achieve the objective of such arrays in the
combinatorial methodology. Accordingly the diameter of the regions
seldom exceeds 15 mm and usually presents regions of much smaller
size. The small size of these regions can pose contamination
problems. Contamination whether detected or undetected can
interfere with the usefulness of such arrays by corrupting the data
obtained from the material samples thereby leading to false
conclusions that waste time and resources. Consequently reuse of a
substrate such as a base that receives material directly on its
surface requires thorough cleaning and/or treatment to avoid the
presence of any contaminants from previous experiments. Since the
regions are by definition small, intensive and thorough cleaning of
the small areas can present a challenge. Moreover the composition
of the substrate or base may exacerbate the problems. The use of
easily machinable or formable materials facilitates the manufacture
of the small structures on the surface of the base that define the
vast number of small regions needed for such arrays. However easily
machinable and formable materials are typically less susceptible to
the harsh conditions needed to get the contaminants out of the
small regions.
[0005] It is already known to synthesize a multitude of material
samples in arrays of small vessels. For example, it is known to
produce various metal oxides in small vessels having the form of
individual crucibles retained by a base. The use of individual
vessels allows their disposal or intensive cleaning once all
experimental steps with the material contained therein are
concluded. However, many of the synthesis operations, treatments
steps and analysis of a material may require movement of the
arrays. So on one hand the vessels must remain fixed in the base
throughout such procedures that may in addition to movement between
pieces of equipment require shaking stirring or agitation in the
equipment. But at the same time the vessel must not become so fixed
in the base or substrate that they are not readily removed for
disposal. Fitting vessels into a base with a tight tolerance may
prevent their removal after completion of the experiment. Moreover,
certain treatment steps may create minor distortion of the vessels
or the base that binds them together by the completion of the
experiment.
[0006] Such conditions occur in the synthesis of many materials.
One example of such materials, zeolites, are prepared by so-called
hydrothermal synthesis at temperatures ranging from 100.degree. C.
to 200.degree. C. requiring crystallization times of one hour or
more. For syntheses being carried out at temperatures that are
higher than the boiling point of the solvent, it is necessary to
use pressure vessels, and these have to be suitable for the
temperature and pressure used during the operation. This further
requires the sealing of the vessels in a manner that prevents
contamination between the materials undergoing synthesis.
[0007] Zeolite syntheses are usually performed in strongly alkaline
media, often at pH>14, and the reaction mixture will often
contain toxic chemicals such as, e.g., fluoride. Conventionally,
syntheses that may be performed at temperatures lower than
110.degree. C. are carried out in polymer bottles, often Teflon.TM.
(tetrafluoroethylene), while reactions at higher temperatures
require steel autoclaves, perhaps lined with Teflon.TM.. Having a
cost effective combinatorial method for such syntheses is quite
useful since he price of an autoclave of this type with the
required safety details is typically of the order of about 1,000
United States dollars or higher. Furthermore, such an autoclave
will weigh from 1 kilogram and upwards, and all of these elements
represent limitations regarding the number of syntheses that may be
performed in most laboratories in the course of one year.
[0008] Zeolite synthesis is often carried out by keeping the
synthesis mixture at around 100.degree. C. for at least 6 h. At
these moderate temperatures sealed chambers are necessary in order
to avoid drying out of the synthesis mixture. US 3,130,007 A
exemplifies conventional zeolite synthesis. Common to all the
synthesis procedures mentioned and for all other known synthesis
procedures for the preparation of zeolites on a laboratory scale
with the purpose of discovering new zeolites or to optimize
existing zeolites is that these are performed in a cumbersome and
expensive manner by having to separately prepare each reaction
mixture, which typically consists of 4-7 reagents, and by adding
the reagents one by one. In many other examples the is synthesis of
zeolites and other molecular sieves needs temperatures well above
100.degree. C., so that steel pressure vessels or the like are
required.
[0009] New, combinatorial techniques which may be used for liquid
phase synthesis at temperatures above approximately 100.degree. C.
have been disclosed in WO 02/07873 that provides the synthesis to
be performed in a hermetically sealed vessel at elevated pressures.
There is, e.g., a known design called "multiblock", see Krchnak,
V.; Vagner, J. Peptide Res. 1990, 3,182, consisting of i) a
Teflon.TM. block holding 42 reactors, polypropylene syringes
equipped with polymer filters, ii) a vacuum adapter connecting each
reactor to a vacuum line (not described in detail) which enables
rapid washing in an apparatus for continuous flow, iii) two
Teflon.TM. plates with 42 stoppers to which the Teflon.TM. block is
fastened during use, and iv) a glass cover used during
homogenization. The problem with this design is that the reactors
which are made of glass and which do not have protected sidewalls
may be used only at low pressures and not in strongly alkaline
solutions.
[0010] Until recently there has been no available literature
describing methods or equipment for using arrays that might be used
for practical work to sufficiently retain vessels in the array to
perform combinatorial experimentation while providing facile
withdrawal of the vessels for replacement in the substrate or base.
Zeolite synthesis can be particularly problematic inasmuch as such
syntheses almost without exception require hydrothermal treatment
of a solution or gel with a relatively high content of water and
often high contents of organic compounds in a closed chamber under
elevated temperatures and high pressure.
[0011] WO 98/36826 discloses a system for screening of synthesis
conditions for the preparation of zeolites and other non-carbon
materials requiring hydrothermal conditions in the temperature
range of 100.degree. C. to 250.degree. C. Some of the parameters
that have been made more cost efficient with the multiautoclave of
WO 98/36826 include: reduced size of the separate reaction chambers
and increased number of reaction chambers; reduced use of
reactants; automated addition of reactants, for instance by a
pipetting machine which makes quick and exact addition of all
liquid reactants possible; and devices allowing automated analysis
with X-ray diffraction and automatic identification of known
crystalline phases. WO 98/36826 has also disclosed automated
equipment for larger synthesis series and preparation formulations
based on mixtures of different liquids/solutions with varying
reactant ratios.
[0012] The WO 98/36826 invention is a pressure and temperature
reactor vessel comprising a central block having a multitude of
perforations. The perforations are through-going perforations,
cavities or other form of holes permanently closed at one end. A
cover engages the central block to seal the open ends of the
perforations and form a multitude of chambers. A sealing means,
operatively associated with the cover together form a pressure
tight seal when a locking means holds cover in engagement with the
sealing means to make reaction chambers pressure tight.
Applications for the WO 98/36826 invention may, in addition to
zeolite synthesis, be in any field of activities within research
and development connected to products where at least one production
step comprises the mixing of different liquids, e.g., in the fields
of organic and inorganic syntheses, paint production, formulation
of fuels, food industry, etc., and, furthermore, applications
within clinical testing, dissolution and digestion of samples with
acid etc. where a liquid reactant is added to a liquid or solid, or
a solid is added to a liquid. The invention of WO/9836826 is most
useful where open vessels cannot be used, and where it is required
to operate at temperatures which will cause elevated pressures in
the liquid part of the mixture.
[0013] The present invention is an advancement in the art as
compared to WO/9836826 in that a set of vessels are removably
secured within associated bores defined by a base. The vessels are
constructed of material that is inert in the reactions or
treatments conducted within a synthesis zone including a pressure
and temperature conditions as may occur when using and substrate or
base in any form from simple plate to a multiautoclave. The
vessels, being each a single unit, line the interior of the bores,
both the interior walls and one end. The vessels allow for a simple
means of extracting material from the multiautoclave and can then
be replaced with fresh vessels to minimize cross contamination
between runs using the vessels. Optionally, the vessels may be used
in the weighing of reagents such as powders and liquids for
increased accuracy. Others have employed a liner in specific single
vessel units such as U.S. Pat. No. 4,554,136 A where a
fluoropolymer lining is used to inhibit acid corrosion of the walls
of the pressure vessel, U.S. Pat. No. 3,048,481 A which discloses a
refractory lining used within a synthesis gas generator, and U.S.
Pat. No. 3,396,865 A which teaches a synthesis pressure vessel
having a thermally conductive pressure shell and a chemically
resistant thermally insulating lining within the shell made of a
dense refractory concrete. The present invention, however, is
unique in its use of a set of vessels to facilitate solid product
removal and minimize cross contamination between runs using the
array of vessels.
SUMMARY OF THE INVENTION
[0014] The invention allows the making of arrays of materials in
quantities suitable for research and development using vessels that
are easily maintained in array during the experimentation steps and
may be discarded the array once the experimentation is completed.
The invention overcomes the problems of using a plurality of small
vessels in a method or apparatus where the problems of adequately
securing the vessels for manipulation during experimentation while
also removing stuck vessels from the array are both overcome. In
one form the invention introduces a component of a first material
into one independent vessel through an opening in its top of the
first vessel and introduces another component of a second material
into a different independent vessel through its top. Both vessels
are removably located about a base at different first locations.
Transformation of the components in the vessels then occurs to
produce different materials therein. After completion of the
experiments a displacement medium simultaneously urges the vessels
from their respective locations about the base for discard or reuse
after any necessary cleaning. Typically at least one property of
the materials from the vessels is determined either within the
vessel or after recovery of the materials.
[0015] It is also possible to practice the invention without the
use of a base per se by again introducing the component of first
and second materials independent vessels. In this case one of the
independent vessels is removably located about one opening in a
framework at a one location and another of the independent vessels
is removably located about another opening in the framework at a
different location. The vessel and framework locations permit
contact by the framework with a portion of each vessel. In this
form the invention also provides a unique trapping surface for
contact with a different portion of each of the vessels when in
their framework locations. Urging the trapping surfaces in unison
into contact with the vessels create trapping contact between the
vessels and the framework thereby fixing the location of the
vessels relative to the framework for the manipulation of the
arrays during the steps of experimentation. The components in the
vessels are transformed to produce materials for experimentation in
the desired array using one or more steps. After the steps, urging
the first and second trapping surfaces out of contact with the
first and second vessels permit ready withdrawal of the first and
second vessels from the framework. In most cases the framework will
comprise provided a base with bores for receiving the vessels but
the framework may simply comprise an grid of openings through which
the vessels pass in part.
[0016] In another form the invention provides a method of making an
array of materials by introducing at least one component of a first
material into a first vessel; introducing at least one component of
a second material into a second vessel; and removably securing said
first vessel at first location within a first bore defined by a
base and removably securing said second vessel at second location
within a second bore defined by the base by interaction between a
surface of each vessel and a wall of its respective bore. The
components in the first vessel are transformed into the first
material and the components in the second vessel are transformed
into the second material. At least a portion of the first material
is recovered in isolation from the second material. In one
embodiment of the invention, at least the first vessel is tapered
to provide the interaction between only a portion of an outer
sidewall of the first vessel and the inner wall of the first bore.
In a more limited embodiment of this form, at least a plurality of
the bores extend completely through the base, each bore retains a
vessel and the plurality of bores are closed at their distal ends
to at least temporarily create a pocket by affixing a bottom
closure to the base that covers the distal ends of the bores and
optionally removing the bottom closure permits at least partial
displacement of the vessels through either side of the bore that
removably secures it. Optionally this embodiment of the invention,
may provide a displacement medium in the form of a series of
displacement pins affixed in pattern that aligns a pin with each
distal end of the plurality of bores. After the removal of the
bottom closure the pins displace the vessels from the bores by
contact of an individual pin with a bottom of each displaced vessel
as the pins are urged into the bores.
[0017] The invention can also comprise a unit containing a
multitude of pressure vessels, also referred to as a
multiautoclave. The multiautoclave has typically from 10 to 10,000
or more small, separate chambers that retain a vessel, each
typically with a volume of from 0.001 to 10 ml. The multiautoclave
may be composed of a base having bores that define the chambers and
optionally extend completely through the base. Where the bores
extend partially through the base a single plate will cover the top
to maintain pressure within the vessels. When the bores extend
completely through the base a set of plates will cover opposite
faces of the base. Each vessel is removably secured within a bore
of the base and optionally a thin laminate may be sandwiched
between the base and either plate to improve the pressure seal.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a perspective view of a base with bores.
[0019] FIG. 2 is a plan view of the base of FIGS. 1 and 2.
[0020] FIG. 3 is a section of the base of FIG. 2 taken along
section 3-3.
[0021] FIG. 4 is perspective view of the underside of the base of
FIGS. 1-3.
[0022] FIG. 5 is a perspective view of a vessel for use in this
invention.
[0023] FIG. 6 is a front view of the vessel of FIG. 5.
[0024] FIG. 7 is an optional cap for sealing the vessel of FIGS. 5
and 6.
[0025] FIG. 8 is a front view section of the cap of FIG. 8.
[0026] FIG. 9 is a perspective view showing the base of FIGS. 1-4
retaining a plurality of the vessels of FIGS. 5-8.
[0027] FIG. 10 is a perspective view of an optional lid for sealing
the vessel and base assembly of FIG. 9.
[0028] FIG. 11 is a perspective view of the assembled base and lid
of FIGS. 9 and 10.
[0029] FIG. 12 is a sectional view of a base showing different
vessel and optional lid configurations for use with the
invention.
[0030] FIG. 13 is a perspective view of a displacement medium
comprising a jig and aligned pins.
[0031] FIG. 14 is perspective view of an alternate base
configuration having shallow bores.
[0032] FIG. 15 is section representative of the base of FIG. 14
having vessels therein and an optional lid configuration.
[0033] FIG. 16 is a section showing an alternate arrangement for
the base section of FIG. 15.
[0034] FIG. 17 is a section of alternate base, vessel and lid
configuration.
[0035] FIG. 18 is a perspective view showing an assembly of a
framework and with trapping surfaces to retain vessels and effect
their simultaneous withdrawal.
[0036] FIG. 18a is a perspective view of the framework of FIG. 18
isolated from the assembly of FIG. 18.
[0037] FIG. 18b is a perspective view of the trapping surfaces of
FIG. 18 isolated from the assembly of FIG. 18.
[0038] FIG. 18c is a perspective view of the framework of FIG. 18
isolated from the assembly of FIG. 18 and retaining vessels.
[0039] FIG. 19 is section representative of FIG. 18 with the
trapping surfaces in a first position relative to the
framework.
[0040] FIG. 20 shows the trapping surfaces of FIG. 19 in a second
position relative to the framework.
DETAILED DESCRIPTION OF THE INVENTION
[0041] As summarized above, the invention is a method of making an
array of materials. The method uses at least a first and second
vessel. The vessels are described below in greater detail. It is
preferred that a greater number of vessels be used in order to
enhance the efficiency of the method. Eight, sixteen, forty-eight,
ninety-six, or a greater number of vessels may be used. The number
of vessels may extend into the hundreds, thousands, or ten of
thousands. The vessels are removably located about a base or
framework.
[0042] FIG. 1 shows a perspective view of one embodiment of a base.
The base 22 defines a multitude of bores having openings 24 in the
top of the base for receiving vessels. When the base is to be used
at temperatures in the range of from about 150 to about 250.degree.
C., the base may be made from stainless steel, aluminum, titanium
or other rigid material such as polyethylethylketone (PEEK) or the
like. For use at temperatures above 150.degree. C., the base 22 can
be made entirely of Teflon.TM., for use below 130.degree. C. it can
be made of polypropylene, and for use below 105.degree. C. it can
be made of polyethylene. It is preferred that the bores be
through-going, or in other words, the bores extend from one surface
of the base to a parallel second surface of the base. However, as
can be seen in FIG. 2 the openings 24 of the bore define a passage
through the thickness of base 22, but only a smaller diameter port
26 to the bottom of base 22. Port 26 provides one form of release
opening for use with a displacement medium as hereinafter
described. The difference in the diameter of the openings of the
bores 24 and the ports 26 are shown in FIG. 3 as well as the depth
of the opening 24 through the thickness of base 22. FIG. 4 shows
port 26 opening in the bottom of base 22. Alternatively, the bores
may define cavities that do not have an opening extending
completely through the base. In general, the invention will be
described below as the preferred embodiment of a base having bores
with bore openings on one surface of the base and ports connecting
the bore openings to another side of the base.
[0043] FIG. 5 is a perspective view looking into a typical vessel
28 that occupies at least a portion of the bores in the base. The
vessels may conform to the shape of the bores of the base and are
positioned so that an individual vessel extends into at least one
of the bore openings 24. FIGS. 5 and 6 show a cylindrically shaped
vessel 28. FIG. 6 shows the outline of the interior of vessel 28
and an optional removed dimple 32 from the bottom of the vessel to
aid in withdrawal of the vessel. The individual vessel lines at
least a portion of the walls of the bore opening 24 and lines the
bottom of the bore opening near port 26. Alternate vessels are
possible and are discussed in more detail below. The vessel is
preferably made of an inert polymer material such as Teflon.TM.,
polyethylene, polypropylene, perfluoroalcoxy fluorinated ethylene
propylene, and polyethylethylketone, that is able to withstand the
temperatures and pressures necessary for synthetic reactions. The
vessels may be constructed of material that is transparent to
radiation for ease of later analysis, such as transparent to
infrared radiation or transparent to x-rays. However, the vessels
themselves may provide a convenient way to provide catalyst
function to the reaction occurring within the vessel. For example,
catalyst may be present on the interior surface of the vessels, may
be released from cavities within the walls of the vessels, may be
released from an adsorbent that coats the walls of the vessels, and
the like.
[0044] In one embodiment of the invention, materials are made in
quantities suitable for research and development experiments. For
example, material may be made in quantities ranging from milligrams
to grams. The vessels in this application may have a maximum inner
diameter of about 10 mm. Multiple vessels are used in an
application, and typically, 8, 48, 96, 188 or more vessels are
removably located about a base.
[0045] The vessels provide several advantages over previous
equipment with the most important being the simple means of
removing the vessel from the base. This allowed for a greater
degree of flexibility in that different vessels may be grouped for
different types of experiments. Another benefit is the ease of
extracting solid products from the separate reaction vessels as
compared to extracting multiple solid products from a unitary
device. Yet another advantage is the significantly reduced chance
of cross contamination between runs using the multiple pressure
vessels. Small vessels may improve operations by eliminating the
need to clean small confined regions on plates and thereby
eliminating the risk of undetected contamination compromising
future experiments. The individual vessel may also be used to weigh
the reagents and or products to a high degree of accuracy. The
vessels may also provide an alternative approach to product
recovery through using ports 26 in the base 22. Vessels containing
synthesis products may be pressed out of the bores of the base
using an extraction device which is discussed in greater detail
below.
[0046] At least one component of a first material is introduced
into a first independent vessel, and at least one component of a
second material is introduced into a second vessel. The components
may be introduced serially to each of the vessels, or
simultaneously to the respective vessels. Additional components may
also be added to one or more of the vessels. Multiple components
may be mixed together and added to a vessel, or may be introduced
to the vessel separately. When multiple components are each
introduced to a single vessel separately, the multiple components
may be introduced sequentially or simultaneously. The same or
differing amounts of components may be introduced to the vessels.
The materials may be inorganic or organic. Preferred materials
include zeolites, ceramics, composite materials and the like. The
term different materials is meant to include materials produced
from the same components. For example, varying the amounts of the
components or the order of addition of the components, although the
identity of the reactants remains the same, may results in
different product materials.
[0047] Various different techniques may be used to introduce the
components to the vessels, such as manual methods and automatic
methods. The components are preferably introduced to the vessels in
measured amounts, the measuring may be contemporaneous with the
introduction, before the introduction, or after the introduction.
One embodiment may use a dispenser such as a pipette, micropipette,
or a powder doser. It is preferred that the dispenser be automatic,
but is not necessary.
[0048] The components are transformed, while in the vessels, into
materials having at least one property that is different from that
of the starting component. It is expected that the transformed
materials between at least two of the vessels would have at least
one property that is different.
[0049] FIGS. 7 and 8 show an optional lid that may cover the top of
the vessel. FIG. 7 shows the outline of an hollowed portion 36 on
the interior of a lid 34. Lid 34 may be inserted into the opening
of interior portion 30 of vessel 28. Lid 34 may be shaped with a
tapered end 33 to facilitate the insertion of lid 34 into interior
portion 30 of vessel 28. Lid 34 may also have top portion 35 to
prevent lid 34 from completely inserting within interior portion 30
of vessel 28. One purpose of lid 34 is to retain the components and
materials within the vessel during handling, processing, and
transformation. Another purpose of lid 34 is to provide closure of
the vessel for purposes of maintaining an internal pressure such as
that required for hydrothermal synthesis. Lid 34 may be constructed
of materials as described for the vessel and the base above.
[0050] FIG. 9 shows a plurality of vessels 28 and lids 34 assembled
into a base 22. and FIG. 10 shows a retaining plate 38 that
contacts the lids to urge the bottom of vessels 28 into contact
with the bottom of the respective bores in base 22 when assembled
with the base of FIG. 9 into the assembly shown in FIG. 11.
Retaining plate 38 may also operated to urge a portion of lid 34
into the interior portion of vessel 28. The lids may actually be an
integral part of the retaining plate, or the retaining plate may
retain a separate lid for each vessel that has a lid. The vessels
28 are removably placed within bore openings 24 defined by base 22.
The vessels may be removably placed about the base before, during,
or after the components have been introduced. The vessels may be
removably placed about the base sequentially, at the same time, or
in groups. In one embodiment, a bore contains no more than one
vessel. The term about a base is meant to include within, on, or
against the base.
[0051] Optionally, retaining plate 38 may be fixed to base 22 using
clamps or fasteners. Threaded fasteners may operate through bores
in retaining plate 38 and corresponding bores in base 22 to
maintain the assembly during handling and processing.
[0052] The retaining plate serves several functions. The retaining
plate in combination with the lids provide for a mechanism for
independently sealing each of the vessels in order to retain
materials within the vessels during mixing operations such as
shaking, vibrating, stirring, tumbling, and the like. Furthermore,
with each vessel being independently sealed, the components within
a vessel may be mixed without resulting in cross contamination
between different vessels. One possible feature of the invention
employing one or more retaining plates is that a large number of
assemblies may be placed on top of each other forming layers of
reaction chambers according to the desired capacity. As an example,
ten assemblies as shown in FIG. 11 can be placed on top of each
other. The retaining plate, or the lid, or the combination of the
retaining plate and the lid may also operate to provide pressure
that prevents the vessels from rotational movement with respect to
the base, or the retaining plate may operate to prevent the vessels
from any movement with respect to the base.
[0053] FIG. 17 more completely illustrates the use of fasteners in
the form of bolts 48 that extend through a hole 52 in a top
retaining plate 38', a hole 54 in a base 58 that defines through
going bores 60 and a hole 56 in a bottom retaining plate 46. The
bolts 48 engage nuts 50 to secure the whole assembly together once
vessels 62 are ready for sealing. To facilitate work with the
vessels before closing retaining plate 38' optional bolts 64 may
pass through holes 66 and engage a threaded hole 68 in base 58 to
secure it to the base while moving the open ends of vessels 62 in
base 58 to the various locations required for the experimentation
steps.
[0054] The invention is suitable for use with a wide variety of
base, retaining plate and vessel configurations. FIG. 17 also
demonstrates the use of vessels 62 having lips 70 that extend
radially outward over the top of base 58. These lips have a
thickness much less than the depth of vessels 62. Securing
retaining plate 38' to base 58 will squeeze lips 70 between the two
contacting surfaces to provide the necessary seal to maintain
pressure in vessels 62. Preferably the bolts 48 and nuts 50 are
placed in such a manner and their number adjusted so that a
sufficiently distributed even load is obtained in order to ensure
that all the chambers are tight when in use. Additionally the
squeezing mechanism may include springs or the like, which ensures
the maintenance of a suitable pressure. A frame made of a rigid
material that ensures good tightness in the outer chambers may
enclose the entire assembly, also counteracting deformation of
plates made of pure Teflon.TM. or another ductile material.
[0055] FIG. 12 further shows the variety of vessels that can occupy
the bores and use the retaining plate as shown in FIGS. 3 and 17.
At the location of each vessel 28 base 22' further defines ports
26. Retaining plate 38' retains lids 34 in various forms as
described. Vessels 28a have tapered geometries where a closed end
has a diameter less than that of an open end and vessels 28a and
are completely contained within the bores of base 22' with the
exterior surface of the open end of the vessel being in contact
with the surface of the bore. Many closure arrangements can seal
the tops of vessels 28a for retaining pressure. In its simplest
form the underside of retaining plate 38'' may provide sufficient
containment contacting the proximate face of base 22' with enough
force to seal the bore that retains vessel 28a. Placing a gasket or
other thin layer of sealing material between the two contact
surfaces of base 22' and retaining plate 38'' can increase the
effectiveness of the seal across the bores that retain vessels 28a.
Retaining plate 38'' may also provide a direct seal with the top of
vessel 28a using a lid 34' integrated into retaining plate 38' and
extending below its bottom surface such that the bottom of lid 34'
directly contacts the rim of vessel 28a.
[0056] Vessels 28b also have tapered geometries where a closed end
has a diameter less than that of an open end. Vessels 28b, while
positioned within the bore, extend beyond the opening of the bore
in the base. The portion of vessels 28b that extend beyond the bore
28b provide a protruding region of the vessel having an enlarged
outer diameter with respect to the diameter of the bore The
exterior surface of vessels 28b are in contact with the bore
opening and adaptation of such contact into a suitable force-fit
within the bores allows frictional forces to operate against
rotation or other movement such as translational movement of the
vessels during the steps of experimentation. However, the retaining
plate and or lids may also be used to prevent cross contamination
or to contain materials within the vessel during mixing. All of
vessel 28c, 28d, 28e and 28f have a cylindrical geometry. Vessels
28c, 28d, and 28F while positioned within the bore, all extend
beyond the opening of the bore in the base. Retaining plate 38''
may contact the tops of any or all of these vessels to prevent
their movement within bore and if desired provide a pressure seal
between the rim of the vessels and the underside of retaining plate
38''. Although not required, any of the cylindrical vessels may be
force-fit within the bores as described above for the tapered
vessels in order to restrict against rotation or other movement.
For example Vessel 28c may undergo a slight force-fit with the base
22' when inserted in a bore to maintain its position. Vessel 28d
may fit relatively loosely into its respective bore and relies on
contact with surface of retaining plate 38'' to keep it positioned
within base 22'. Vessel 28f is a two-piece vessel comprised of a
bottom disk 72 in combination with a detachable side wall in the
form of a sleeve 74. The sleeve 74 rests on an at least partially
closed bottom 76 of the bore. Pressure from retaining plate 38''
against the top of sleeve 74 urges it into contact with disk 72 so
that sidewall section and bottom section function as a unitary
vessel while optionally provided a seal at the top of sleeve 74
with the underside of retaining plate 38''.
[0057] As with the unitary vessels, vessel 28f may be contained
within the bore, or may extend beyond the bore as shown. As
depicted the bore of base 22' completely contains vessel 28e such
that adjacent lid 14' is partially inserted within the bore to
contact the rim of vessel 28e.
[0058] Using any vessels, force-fitting of vessels, addition of
components to vessels, deformation of vessels undergoing sealing,
exposure to pressure and temperature conditions under
experimentation, and other procedures will create the need to
extract the vessels from the base. Vessels lodged within a bore may
be extracted from the base using a displacement medium. One form of
such a medium is an extraction tool such as that shown in FIG. 13.
Extraction tool 40 has a jig 44 for positioning pins 42 in
alignment with ports 26 of the bores or through going bores 60 in
order to disengage the vessels from the bores. Extraction tool 40
provides for simultaneous disengagement of the vessels from the
bores. In one embodiment of the invention, extraction occurs by
placing a base of the type shown in FIGS. 1-4 or 17 that contains
vessels 28 or 62 within the bores over the extraction tool and
forcing it downward so that pins 22 enter either the open bore or
ports 26 and contact vessels 62 and 28. Continued force would
result in disengagement of the vessels from the bores of the
base.
[0059] Many alternate forms of a displacement medium for removing
more than one vessel at a time from the bores are within the scope
of the invention. For example, another form of mechanical
displacement medium could manually mechanically seize at least a
portion of several vessel about a surface of each vessel to
withdraw the seized vessel from its bore. If the vessel is formed
of relatively soft material such extractor could use an array of
hooks or puncturing devices to penetrate an interior or exterior
surface of individual vessels as moves toward the block and then
simultaneously remove the engaged vessels as it is withdrawn. Other
forms of mechanical displacement mediums may engage a lip, tab
other member on the vessel to withdraw it from the base. For
instance a series of thin members may slide under the lip 70 of the
vessels as shown in FIG. 17. In one form such a removal device can
simply comprise an extractor in the form of a flat plate with
enlarged openings that fit around the outer edges of lips 70 and of
suitable thinness to slide under the lips 70 when urged against
them for lifting of the vessels from the base with the plate. Such
a surface fluidic or electro mechanical displacement medium may
also find use in this invention. For example with the use of
ferrous vessels a magnetic field may provide the displacement
medium to attract or repel the vessels from a block. More simply
the displacement medium can comprise a compressed gas such as air
delivered to one side of through going bores 60 or ports 26. An
open chamber sealed around the bottom perimeter of a block 22 may
deliver the air. Alternately, an additional block 22 in the form of
that shown in FIG. 4 may serve as manifold which when in bottom
side to bottom side contact with a similar block 22 delivers
compressed gas out of its ports 26 and into corresponding ports 26
of the similar block to blow the vessels from the bores that retain
them. Similarly the a block 22 can serve as a vacuum manifold by
placing its bottom over the top of a similar block 22 that retains
vessels and drawing a vacuum between the individual vessels and the
ports 26 as the two block are maintained in at least partially
sealed contact. Drawing the vacuum can either merely dislodge the
vessels extraction by an additional displacement medium or
maintaining the vacuum between individual vessels and ports 26 may
allow complete withdrawal of the vessels with removal of the block
22. Thus the displacement medium can comprise any effective force
delivered to the vessels to effect displacement of withdrawal of
more than one vessel at a time.
[0060] The array of vessels need not extend significantly into a
bore or into a bore at all to utilize this invention. FIGS. 14-16
illustrate shallow depressions 80 with optional holes 82 or simply
holes 84 on different regions of base 78. Depressions 80 and holes
84 can retain the vessels 86 or 86' (shown in outline) in place on
the regions. The size of holes 80 may permit a force fit with the
outside wall of vessel 86 to retain the vessels on the plate.
Blowing compresses gas through the optional holes 82 can again
serve as a displacement medium to eject the vessels 86 from
depressions 80. Alternately placing vessels 86 with a relatively
loose fit into the depressions 80 and then drawing and maintaining
a vacuum through the optional holes 82 can provide the retaining
force for the vessels. In such an arrangement releasing the vacuum
through holes 82 also releases the vessels such that the absence of
the vacuum serves as the displacement medium. The use of the vacuum
displacement medium can eliminate the need for depression 80
altogether where sufficient retention is possible by merely drawing
the vacuum through holes 84 to create enough force to retain vessel
86' directly on the surface of base 78.
[0061] To use another form of displacement medium the vessels 86 or
86' can comprise a ferrous material and the area of holes 82 or 84
can serve as point contacts in an array of electro-magnets that can
contain vessels 86 or 86' on the base until release of the vessels
by de-energizing the magnets. In another embodiment base 78 can
comprise one large electromagnet for retaining ferrous vessels that
thereby eliminates the need for any holes or depressions.
[0062] FIG. 15 shows a section that further illustrates all of the
foregoing description of the vessel and base interaction along with
additional forms of displacement mediums. On the far right FIG. 15
shows a vessel 86' retained on the top of the base 78 by connection
with a source of vacuum through hole 84. Next, to the left in FIG.
15 a vessel 86 resides in a depression 80. Again vessel 86 may have
a force-fit with depression 80 in which case hole 82 can
accommodate a mechanical or pneumatic displacement medium to force
vessel 86 and several similarly situated vessel from depression 80
when desired. Alternately vessel 86 may fit relatively loosely into
depressions 80' not having optional hole 82 retains vessels 80 in a
force fit as previously described and hole 86 may retain the vessel
86 selectively in place through vacuum or other means. An offset
retaining plate 90 contacts the top of the vessels 86 and retains
them in depressions 92. Securing offset retaining plate 90 by
threading bolt 94 into threaded hole 96 of base 78 provides
additionally stability to the base and vessel assembly for
transport vessels and/or agitation of the materials contained
therein and can also provide sealing of the vessels for pressure
operations. Retaining plate 90 in combination with the depressions
92 may provide another form of mechanical displacement medium when
unbolted from base 78 by using the plate 90 to simultaneously tip
two or more of vessels out of depressions 80' thereby eliminating
the need for any other displacement medium.
[0063] In a similar manner to that just described it is also
possible to use the same displacement medium for removing
relatively rigid vessels from a relatively pliant and preferably
elastic base wherein the base permits most of any necessary
deformation to retain the vessels in a force-fit. Release of the
vessels, in this instance while possible using many of the
different displacement mediums as already described, may again
simply rely on engagement and tipping of the vessels from the base
using a grid for simultaneous contact of the vessels. A framework
120 or trapping plate 108 as later described are examples of such
grids that can engage the tops of the vessels for tipping from the
base.
[0064] Retaining plate 90 may also include ports 98 for
communicating fluids with the vessels 86. A plenum 100 brazed or
welded in place over the top of retaining plate 90 can provide a
sealed chamber 102 for communicating or evacuating fluids from
vessels 86. By pulling a vacuum in the chamber 102 retaining plate
can serve as a vacuum for of displacement medium that permits
simultaneous lifting of the vessels 86 from the depressions 80'.
The chamber 102 can also deliver fluids for treatment or testing of
the materials in the vessels 86. Plenum may be divided as with
individual piping to each divided area to provide any number of
different fluids to groups of vessels 86 or even individual vessels
86.
[0065] FIG. 16 provides another alternate arrangement for situating
vessels 86'' directly on the top of the base 78. Vessel 86'' have
posts 88 depending form their bottoms for insertion into hole 84
that extends completely through base 78 or hole 84' that extends
partially into the base. Post 88 may engage holes 84 or 84' in a
force fit or a loose fit for ejection of the post by mechanical
pneumatic or other displacement medium in the case of a force-fit
and retention by vacuum, magnetic or other retention methods
susceptible to selective de-energizing. Again a retaining plate 90'
may secure the vessels more firmly to the base by use of a bolt 94
and a threaded hole 96. The addition of guide plate 104 for
engagement with the sides of base 78 can further improve stability
enhancing function of retaining plate 90. Retaining plate 90' in
combination with stubs 106 that depend from its underside into
vessels 86'' can provide another form of mechanical displacement
medium when unbolted from base 78 by using the plate 90' to
simultaneously tip the posts from two or more of vessels out of
holes 84 or 84'. Retaining plate 90' may also include ports 98' for
communicating fluids or solids with the vessels 86 and may again
use a plenum in communication with the ports 98'.
[0066] FIGS. 18, 18a, 18b, and 18c illustrate another embodiment of
the invention that uses the release of a mechanical retaining
device to provide the displacement medium. FIG. 18 shows an
assembly 126 of a trap plate 108 having trapping surfaces in the
form of holes 112 positioned over a framework 110 for movement of
the trapping surfaces in unison. As shown in FIG. 18a framework 110
comprises an array holes 116 in a flat plate 118 supported by
sidewalls 120. FIG. 18c show vessel 114' occupying all of the holes
in the 116 in framework 110. Holes 116 have a loose fit for contact
with a portion of the sidewalls of the vessels. The size of the
holes permits their ready insertion and withdrawal from framework
110. Framework 110 can have a hollow interior as depicted in FIG.
18a or may comprise a solid block with bores that extend partially
or completely through the base. Ordinarily framework 110 will have
a bottom plate to prevent the vessel from dropping completely
through holes 116. To complete the assembly plate 108 rests on top
of framework 110 and vessels 114' extend through holes 112 that are
sized to fit readily over the vessels for contact with a portion of
the vessel sidewalls.
[0067] FIGS. 19 and 20 show the relative positioning of framework
110 and trapping plate 108 during for the retention and release of
the vessels 114'. FIG. 119 shows the release position where the
holes 122 of trapping plate 108 align in a relatively concentric
manner with respect to holes 116 of framework 110 to permit ready
insertion and withdrawal of vessels 114'. Positioning framework 110
and plate 108 in this manner allows insertion of the vessels 114'
into assembly 126 individually or collectively through holes 122
and 116. As the vessels 114' are dropped into the assembly they
rest on an optional retaining plate. Simultaneous withdrawal of
multiple vessels 114' from the assembly 126 is effected by either
withdrawing the bottom plate 124 or lifting the assembly 126 to
leave the vessels 114' on the bottom plate 124. The effectiveness
of the pinching action of plate 108 and framework 110 in retaining
vessels 114' allows enlarging sizing of holes 122 and 116 that
eliminates adhering or sticking of the vessels 114' within assembly
126 when it is positioned for release of the vessels as shown in
FIG. 19.
[0068] After insertion of the vessels 114' into the assembly as
shown in FIG. 19, positioning plate 108 and framework 110 in the
relative positions shown in FIG. 20 will retain the vessels in the
assembly 120 for moving of the vessels during the different steps
of experimentation. With vessel 114' in place, sliding plate 108 to
align holes 122 in an eccentric arrangement relative to holes 116
causes trapping surfaces provided by edges of holes 116 to
simultaneously contact portions of the vessel 114' on one side
while on the opposite sides of the vessels opposing trapping
surfaces provided by edges of a holes 122 while simultaneously
contact portions of the vessels on an opposite and at a slightly
higher point on the vessels. The assembly can employ any suitable
clamp detent to hold the relative positions of plate 108 and
framework 110 in the trapping position until the desired release or
removal of vessels 114' from the array.
[0069] The steps used in the transformation of the component or
components contained by the vessels may be any of those commonly
known in the art. Heat may be applied, stirring, mixing, agitation,
hydrothermal conditions, and the like. Multiple steps may be
employed, or a single step may be used, for example, it is often
desirable to calcine inorganic samples after synthesis. Washing,
grinding, and sieving are additional optional steps. Different
components may be added between transformation steps. The materials
formed may be further process or analyzed using different
techniques and are not required to be treated as an array. The
materials are retained in the defined matrix that, in a simple
manner, can be transferred to an automatic sample-switching unit
for analysis, e.g., by X-ray diffraction or IR thermography.
[0070] An added advantage of using the independent vessels is that
the base is ready to be used again with no or only minimal
cleaning. Residue from the previous reactions is removed in the
vessels and the base is virtually residue-free for subsequent
synthesis reactions. The overall benefits of the advances in the
present invention are primarily related to the increase in
efficiency in removing the synthesized materials, the reduction in
cross contamination, and the increase in efficiency in preparing
the apparatus for subsequent use. Advances in the automated layout
will make it possible to more efficiently perform large numbers of
syntheses/formulations simultaneously, and it will thus be very
useful for all research laboratories in industry as well as in
research institutions/universities.
* * * * *